네오니코티노이드계 농약은 전세계적으로 사용되는 강력한 살충제이지만 환경, 생물에 잔류하 여 악영향을 미치고 있다. 이에 본 연구는 네오니코티노이드계 농약인 imidacloprid와 clothianidin이 공시 작물인 알팔파와 적용작물로 고추와 오이를 선정하여 토양처리 및 경엽처리에 따른 꿀벌 독성과 엽상 잔류 량을 비교하여 기존 엽상잔류독성시험법의 문제점을 확인하고자 하였다. Imidacloprid와 clothianidin을 작 물 또는 토양에 권장량 및 배수로 처리하고 시간에 따른 꿀벌의 치사율에 대한 RT25를 확인하고 잎의 잔류 농약을 HPLC로 측정하였다. 그 결과 경엽처리하였을 때 imidacloprid은 공시작물 RT25가 1일 이하, 잔류 량은 1.07 ~ 19.27 mg/kg이나 적용작물은 RT25가 9일 이하, 잔류량은 1.00 ~ 45.10 mg/kg 수준이었다. clothianidin은 공시작물 RT25가 10일 이하, 잔류량은 0.61 ~ 2.57 mg/kg이나 적용작물은 RT25가 28일 이 하, 잔류량은 0.13 ~ 2.85 mg/kg 수준이었다. 토양처리했을 때 imidacloprid와 clothianidin은 공시작물에 서는 꿀벌에 영향을 미치지 않았으며 잔류량은 0.05 ~ 0.37 mg/kg 수준이었으나, 적용작물에서는 imidacloprid은 RT25가 28일 이하였고 잔류량은 4.47 ~ 130.43 mg/kg 수준이었고, clothianidin은 RT25가 35일 이하였고, 잔류량은 5.96 ~ 42.32 mg/kg 수준이었다. 결론적으로 꿀벌 독성과 엽상 잔류량을 작물간 비교하였을 때 공시작물 보다 적용작물이 꿀벌의 치사율에 많은 영향을 미치고 잔류량도 높게 나타났고, 처리방법에 따라 비교하였을 때 적용작물에 대한 토양처리가 경엽처리에 비해 높은 RT25와 잔류량이 나타 났다. 따라서 농약안전성 확보를 위해 제시된 시험법이 실제 적용작물과 농약 처리방법에 따라 차이가 있 을 수 있어 imidacloprid와 clothianidin의 안전성 평가를 위하여 다양한 경로의 연구가 필요하다.
경기도에서 유통중인 포도씨유 50건을 대상으로 잔류농 약 실태를 조사하였다. 50건 중 49건에서 10종의 잔류농 약이 161회 검출되었다. 검출된 농약은 boscalid, cyflufenamid, deltamethrin, difenoconazole, fluxapyroxad, fenpyrazamine, kresoxim-methyl, piperonyl butoxide, tebuconazole, trifloxystrobin 으로 살충제 2종, 살균제 8종이었으며 살균제인 boscalid가 44회, fluxapyroxad가 35회로 가장 빈번하게 검출되었다. 검 출범위는 0.01-1.10 mg/kg으로 모두 포도의 잔류농약 허용 기준 이내로 검출되었다. 검출된 농약의 회수율은 72.6- 129.8%이었으며 검출된 농약의 위해성을 알아보기 위해 %ADI를 산출한 결과 0.0028% 이하로 나타나 포도씨유의 잔류농약으로 인한 위해성은 안전한 수준으로 조사되었다. 그러나 본 연구는 시료의 수가 적고 GC/MS/MS로 분석가 능한 농약만 조사하였기 때문에 보다 신뢰성 있는 결과를 얻기 위해선 앞으로도 꾸준한 추적 조사가 필요할 것으로 사료된다.
과거 약 50년간 국내에서는 화학농약 기반의 병해충 방제가 지속적으로 농업 생산량을 안정적으로 유지시켜 왔다. 그러나 무분별한 화학 농약 사용은 병해충의 약제저항성 발달을 유발하였으며, 이는 기존의 방제효과를 얻기 위해 고농도 살포가 불가피하였으며, 또한 막대한 개발 비용이 필요한 신규 작용점 살충제 개발로 고비용의 방제기술로 전락하게 되었다. 여기에 대부분의 살충제가 신경계에 작용하여 인축 및 비표적 생물계에 영향을 주어 광범위한 사용에 제한을 받게 되었다. 대체 방제기술로 천적과 미생물에 의존하는 생물농약은 방제효율에 서 대부분 화학약제의 수준을 따르지 못해 농민의 절대적 호응을 받지 못하였다. 이 가운데 새로운 패러다임의 생물농약으로 살포용 dsRNA 농약이 화학농약의 방제 효과와 버금가는 시험 농가 반응으로 2023년 12월에 미국 EPA 등록을 받게 되었다. 향후 살포용 dsRNA는 살충제는 물론이고 살균제 및 제초제에 이르기까지 작물보호제 시장 전체에 영향을 미치게 된다. 이에 국내에서도 dsRNA를 실험실 단계에서 산업계 적용 기술 개발 단계로 전환하여야 할 시점에 이르게 되었다.
Honey bee plays an important role in pollinating plants. Recently, however, declines in honey bee populations have been reported in many countries, and pesticides have been pointed out as one of the factors contributing to honey bee loss. To determine the effects of pesticides on honey bee behavior, we investigated the homing ability of honey bee exposed to four pesticides (acetamiprid, imidacloprid, fenitrothion, and carbaryl). In addition, the changes in expression levels of genes associated with ‘learning and memory’ (cGMP-dependent protein kinase foraging, Kruppel homolog 1, Adenlyate cyclase 3, Early growth response protein 1, Hormone receptor 38) were examined after pesticide treatment in forager bee. The four pesticides tested in this study generally reduced the homing ability of foragers. In the examination of gene expression, learning and memory-related genes were induced by the exposure to acetamiprid, imidacloprid, and carbaryl, whereas fenitrothion decreased the expression of these genes in honey bee. Although further studies are needed, this suggests that pesticides may have negative effects on honey bee behavior and behavior-related gene expression.
In this study, we detected the presence of residual pesticides in 341 agricultural products collected from local food outlets in western Gyeonggi Province. Residual pesticides were detected in 105 (30.8%) samples. Six samples exceeded the legal limits for residual pesticides, resulting in a non-compliance rate of 1.8%, which was slightly higher than the average non-compliance rate of 1.4% in the last three years. Among the tested agricultural products, only fruits and vegetables were found to have pesticide residues, with 24 of 34 fruits (a detection rate of 70.6%) and 81 of 277 vegetables (a detection rate of 29.2%) testing positive. In total, 59 types of pesticides, including acetamiprid, which was detected 208 times, were detected and had a detection range of 0.01–2.38 mg/kg. Among the 105 agricultural products containing pesticide residues, a single pesticide was detected in 62 samples (59%) and two or more pesticides were detected in 43 samples (41%). In particular, 14 pesticides were detected in the same sample of peaches; dinotefuran was detected 21 times. Upon examining the toxicity of the detected pesticides, Class III pesticides (moderate toxicity) were detected 44 times (21.2%) and Class IV pesticides (low toxicity) were detected 164 times (78.8%). Class I, II, and III pesticides with fish toxicity were detected 68 (32.7%), 14 (6.7%), and 126 times (60.6%), respectively. Upon examining the exposure to high-frequency pesticide components detected five or more times, the hazard index was found to be ≤2.8%. Accordingly, the hazard of residual pesticides based on dietary intake was deemed insignificant.
The status of residual pesticides was investigated in four pepper seed oil samples and 36 pepperflavored oil samples oil distributed on the market from August to December 2022. A total of 179 pesticides were monitored in 40 samples, and 14 pesticides were detected in 39 of the samples, with a detection range of 0.01-2.16 mg/kg. In chili seed oil, 10 pesticides were detected 27 times with a range of 0.11-2.16 mg/kg, and in pepper-flavored oil, 9 pesticides were detected 94 times with a range of 0.01-0.80 mg/kg. The most frequently detected pesticides were tebuconazole, ethion, and difenoconazole, with ethion being detected in large concentrations in products using Chinese raw materials. Ethion, an unregistered pesticide in the Republic of Korea, has not been detected in the Gyeonggi-do area in the past 10 years. It is thought that the detection of ethion can be utilized as an indicator of products made in China. Peppers are a representative agricultural product for which many pesticides are used, and if the pesticides transferred to pepper seeds are not removed, the probability of detecting various types of pesticides in pepper seed oil is very high. Therefore, continuous research is needed to ensure the safety of pepper seed oil.
To investigate residual pesticide levels in agricultural products contained in Meal-kits, 27 Meal-kit products were collected from marts, Meal-kit shops, and online stores in Incheon City, South Korea. Seventy-six vegetable and thirty-seven mushroom products were analyzed for residual levels of 339 pesticides. Residual pesticides were detected in 23 out of 76 vegetables and were not present in the 37 mushroom products. The residual pesticide detection rate was 20.4% (23/ 113 cases). The pesticides famoxadone 0.034 mg/kg (standard: 0.01 mg/kg or less, PLS) and fenpyroximate 0.302 mg/kg (standard: 0.01 mg/kg or less, PLS) exceeded their maximum residue levels (MRL). This survey revealed that various types of pesticides remain in agricultural products in Meal-kits. Due to the nature of Meal-kit products, there is no separate standard for residual pesticides in agricultural products. Therefore, continuous monitoring of residual pesticides is necessary.
GC-MS/MS using liquid-liquid extraction (LLE) and C18 cartridges was used to identify and quantify levels of chlorpyrifos, chlorpyrifos-methyl, cypermethrin, deltamethrin and permethrin in bulk raw milk. A calibration curve spanning 10 ng/mL to 200 ng/mL was obtained with a satisfactory correlation coefficient of 0.99. The limits of detection (LOD) and limits of quantitation (LOQ) for chlorpyrifos, chlorpyrifos-methyl, cypermethrin, deltamethrin, and permethrin in the matrix ranged from 0.06 to 1.81 ng/mL and 0.19 to 6.04 ng/mL, respectively. The recoveries of 5 pesticides from spiked samples at 37.5-125 ng/mL ranged from 86.1 to 102.1%. The measurement of uncertainty of the GC-MS/MS method for these five pesticides was developed based on the analytical process and quantification. An analysis method that is easier and faster than the method specified in the Korean food standards codes for analyzing these five pesticides in raw material milk was developed. Moreover, the analytical method for chlorpyrifos, chlorpyrifos-methyl, cypermethrin, deltamethrin, and permethrin in bulk raw milk by GC-MS/MS was established.
The honey bee, Apis mellifera, has a defense system, including detoxification, antioxidation, and immunity pathways, against external stimulation such as chemicals, stress, and pathogens. However, pesticides, particularly neonicotinoids and butenolids, have been recently reported to alter physiological changes in honey bee. In this study, we investigated the expression levels of eight genes categorized into detoxification (CYPQ3), antioxidation (CAT and SOD2), and immune system (Abaecin, Apidaecin, Defensin1, Defensin2, and Hymenoptaecin), in five tissues (Head, Thorax, Gut, Fat body, and Carcass) of honey bee treated with three pesticides (Acetamiprid, Imidacloprid, and Flupyradifurone) using quantitative real-time PCR. Gene expression patterns was varied depending on the type of pesticides and tissues. However, among eight genes, the expression levels of CYPQ3 was notably induced, but those of AMPs were generally reduced by all pesticides tested in this study in five tissues. These suggest that CYPQ3-mediated detoxification pathway is induced, but AMP-mediated immune system might be disrupted when honey bee is exposed to neonicotinoids and butenolid.
Pesticides are indispensable in contemporary agriculture but are mainly attributed to honey bee population decline. In order to understand the approximate physiological response to pesticides, honey bees were exposed to seven pesticides (Acetamiprid, Imidacloprid, Flupyradifurone, Carbaryl, Fenitrothion, Amitraz, and Bifenthrin), and expression changes of the genes categorized into four physiological functions (insecticide targets, immune-, detoxification-, and reactive oxygen species response-related gene) were analyzed in the head and abdomen of honey bee exposed to pesticides using quantitative PCR. Based on the heat map analysis, immune-related genes seem to be more up-regulated by pesticide exposure in head than abdomen. Among detoxification genes, only cytochrome P450 families were up-regulated in head. Interestingly, regardless of the insecticide target, expressions of Nicotinic acetylcholine receptor beta 1 and Acetylcholinesterase 1 were notably induced by pesticide exposure in head. Heat map analysis expressing the transcription profiles of various genes in the head and abdomen of the honey bee exposed to various pesticides can be used to diagnose pesticide damage in honey bees in the future.
Due to the concerns over their environmental and health impacts, there have been attempts for shift towards biorational pesticides from synthetic pesticides. Among them, plant essential oils have emerged as promising active ingredients. Due to the complex interactions among their constituents, the bioactivities of essential oils can vary depending on the compositions, which often undermine their stability in efficacy. Here, we present a model-based optimization approach to develop reliable rosemary oil-based biorational pesticide, against two-spotted spider mites, Tetranychus urticae Koch. The ecotoxicity against Daphnia magna and foliar phytotoxicity against Phaseolus vulgaris were also evaluated. Our quadratic models accurately predicted miticidal activity, ecotoxicity, and phytotoxicity. We aimed to maximize, minimize, and minimize these parameters, respectively. We employed seven multi-objective evolutionary algorithms in Matlab. Among them, the nondominated sorting genetic algorithm II with adaptive rotation based simulated binary crossover (NSGA-II-ARSBX) performed best. We experimentally determined the thresholds for miticidal activity and phytotoxicity, based on the current approval process for agricultural pesticide products in Korea. After applying the thresholds, we validated the obtained viable solutions. Our study offers a novel framework to enhance the reliable and responsible use of essential oils as biorational pesticides.
A total of 100 commercially available olive oil products were analyzed for 179 pesticide residues using gas chromatography-tandem mass spectrometry (GC/MS/MS). The olive oil samples were mixed with organic solvents, centrifuged and frozen to remove fat, and pesticide residues were analyzed using the “quick, easy, cheap, effective, rugged, and safe” (QuEChERS) method. The determination coefficient (R2) of the analysis method used in this study was ≥0.998. The detection limit of the method ranged 0.004–0.006 mg/kg and its quantitative limit ranged 0.012–0.017 mg/kg. The recovery rate (n=5) measured at the level ranging 0.01–0.02, 0.1, and 0.5 mg/kg ranged 66.8– 119.5%. The relative standard deviation (RSD) was determined to be ≤5.7%, confirming that this method was suitable for the "Guidelines for Standard Procedures for Preparing Food Test Methods". The results showed that a total of 151 pesticides (including difenoconazole, deltamethrin, oxyfluorfen, kresoxim-methyl, phosmet, pyrimethanil, tebuconazole, and trifloxystrobin) were detected in 64 of the 100 olive oil products. The detection range of these pesticide residues was 0.01–0.30 mg/kg. The percentage acceptable daily intake (%ADI) of the pesticides calculated using ADI and estimated daily intake (EDI) was 0.0001–0.1346, indicating that the detected pesticides were present at safe levels. This study provides basic data for securing the safety of olive oil products by monitoring pesticide residues in commercially available oilve oil products. Collectively, the analysis method used in this study can be used as a method to analyze residual pesticides in edible oils.