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.

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.

In order to provide basic data for preparing management standards and to verify the safety of the Chinese oak mushroom-derived moisturizing medium—which is synthesized and imported in large quantities—the presence of 321 residual pesticides, 7 heavy metals, and 3 radioactive materials was analyzed in the moisturizer samples. Examination of residual pesticides in seven moisturizing medium samples prepared using the Chinese oak mushroom and three domestic sawdust samples used for mushroom culture revealed the presence of cypermethrin and iprodione in three moisturizer samples, but the contents of these pesticides were below the standard limits. Zn was detected in ten samples, Cu was detected in nine samples, and Ni was detected in four samples, but their contents were below the standard limits. Pb, Cd, Cr, and Hg were not detected in any sample. No radioactive materials were detected in the samples. In addition, fruiting bodies of the oak mushroom were observed in each medium. Examination did not reveal the presence of any residual pesticides or harmful compounds. In this study, the use of the moisturizing medium prepared using the Chinese oak mushroom was found to be safe. As residual pesticides, heavy metals, and radioactivity—even in trace amounts—remain concentrated in the human body, continuous verification of the safety of hazardous substances and pollutants during the systematic cultivation and management of these mushrooms is required.

본 연구는 2021년 2월부터 7월까지 잡곡 106건을 수거 하여 잔류농약 실태조사를 하였다. 대형, 중소형 및 온라 인 유통매장을 중심으로 국내 잡곡 40건과 수입 잡곡 66 건을 수거하였고, GC/MSMS, GC/ECD, GC/NPD, LC/ MSMS, UPLC/PDA, HPLC/FLD를 이용하여 다종농약 다 성분분석법으로 잔류농약 341종을 분석하였다. 잔류농약 이 검출된 잡곡은 대형유통매장 1건, 중소형 유통매장 2 건, 온라인 유통매장 5건으로 총 8건(7.5%)이었고, 5건 (4.7%)에서는 농약잔류허용기준을 초과하였다. 이들 잡곡 에서는 MGK-264, chlorpyrifos, thiamethoxam, malathion, piperonyl butoxide, pirimiphos-methyl 등 6종의 농약 성분 이 검출되었다. 검출된 잡곡은 강낭콩(1건), 녹두(6건), 수 수(1건)이다. 검출된 잡곡 중 농약잔류허용기준을 초과한 품목은 수입 녹두(5건)로 미얀마산이었고, 초과한 농약 성 분은 thiamethoxam이었다.

PLS 제도가 모든 농산물을 대상으로 확대됨에 따라 잔류허용기준이 설정되지 않거나 허가되지 않은 농약에 대해서 일률적으로 0.01 mg/kg의 잔류허용기준을 적용하기 때문에 농약 시험법의 정량한계 수준은 0.01 mg/kg 이하를 만족시켜야 한다. 현재 식품공전에 존재하는 7.1.4.12 디메티핀 시험법은 정량한계가 0.05 mg/kg이며 7.1.3.2 디클 로르보스 등 19종 시험법은 정량한계가 존재하지 않는다. 그리고 두 시험법 모두 전처리 과정 중 벤젠을 사용하여 인체 및 환경에 유해할 뿐 아니라 충전칼럼을 사용하여 노후화되고 복잡하다는 단점이 있다. 본 연구는 전처리 과정에 벤젠을 사용하는 성분 중 대체 시험법이 존재하지 않는 5종을 선별하여 다른 용매로 대체하고 QuEChERS 법을 적용하여 0.01 mg/kg의 정량한계를 만족하는 동시시험법을 마련하고자 하였다. 대상성분들의 물리·화학적 특성을 고려하여 QuEChERS법을 이용한 최적 추출·정제법을 선정하여 LC-MS/MS를 이용한 분석법을 확립하고자 하였다. 수용성 유기용매인 1% 아세트산 함유 아세토니트릴을 추출용매로 사용하고 무수황산마그네슘 및 아세트산 나트륨을 첨가하여 추출법을 최적화하고 d-SPE 흡착제를 통해 추출물 중 간섭물질을 효과적으로 제거하여 최적 정제조건을 확립하였다. 결정계수(R2)는 0.99 이상으로 높은 직선성을 보여주었고, 검출한계 및 정량한계는 각각 0.003, 0.01 mg/kg으로 높은 감도를 나타내었다. 대표 농산물 5종 (현미, 감자, 대두, 감귤, 고추)에 대하여 정량한계, 정량한계 10배 및 정량한계 50배 수준으로 처리한 다음 회수율 실험을 한 결과 평균 회수율이 디메티핀은 90.8-114.1%, 디클로르보스는 96.0-113.5%, 오메토에이트는 79.8-119.3%, 클로르펜빈포스는 97.3-107.6% 그리고 아진포스메틸은 74.2-117.7%이었으며 상대표준편차는 모두 14.6% 이하로 확인되었다. 또한 실험실간 검증 결과 두 실험실간 회수율 평균값이 디메티핀은 94.5-108.7%, 디클로르보스는 92.6- 112.8%, 오메토에이트는 74.7-116.1%, 클로르펜빈포스는 98.7-110.7% 그리고 아진포스메틸은 80.9-117.7%이었으며 상대표준편차는 모두 18.4% 이하로 나타났다. 본 연구는 국제 식품규격위원회 가이드라인(Codex Alimentarius Commission, CAC/GL40)의 잔류농약 분석 기준 및 식품의약품안전평 가원의 ‘식품등 시험법 마련 표준절차에 관한 가이드라인 (2016)’에 적합한 수준임을 확인하였다. 따라서 본 연구에서 개발한 시험법은 농산물 중 잔류할 수 있는 디메티핀 등 5종의 안전관리를 위한 공정시험법으로 활용 가능할 것이다.

The content of harmful materials was investigated for coffee beans sold in Daejeon. Total 79 samples were analysed and 213 residual pesticides and 2 heavy metals were analysed simultaneously by GC-MS/MS, GC-NPD, GC-ECD, LC-MS/MS and ICP-MS. The instrumental method was validated with limit of detection (LOD), limit of quantification (LOQ), the linearity of standard curves. LOD of the residual pesticides was between 0.0003 to 0.0021 mg/kg, LOQ of the residual pesticides was between 0.0008 to 0.0064 mg/kg. LOD of the heavy metals was between 0.0077 to 0.0079 μg/kg, LOQ of the heavy metals was between 0.0233 to 0.0239 μg/kg. The linearity correlation coefficient for the calibration curve was between 0.9929 to 0.9999 and the recovery rate was between 95.4% to 106.1%. According to the monitoring of residual pesticides and heavy metals, no pesticide was detected in all coffee bean samples. 88.6% (70 samples) of analysed total 79 coffee beans contained at least 1 heavy metal but there was no sample which exceeded the maximum residual limit. Risk assessment was also carried out based on the content of heavy metals detected in coffee beans. The carcinogenic risk assessment to heavy metals showed that all cancer-risk (CR) values were below 10–6 and it meant that the CR due to heavy metals intake was evaluated as safe. The non-carcinogenic risk assessment to heavy metals showed that all hazard index (HI) were below 1, which was considered acceptable at the current level of exposure. The %PTWI values of lead and cadmium for 55 roasted coffee bean samples were 0.09% and 0.04% respectively, compared with the reference values. This results indicate that there is almost no health risk from heavy metal intake through the consumption of coffee beans in circulation in Daejeon.

2018년과 2019년에 서울에서 유통 중인 건고추 및 고춧가루에 대해 잔류 농약 안전성 검사를 실시하였다. 총 101건의 시료에 대해 71종 농약을 모니터링한 결과 잔류허 용기준을 초과한 시료는 없었으나 잔류농약이 검출된 시료는 87건으로 86.1%의 검출률을 나타내었다. 건고추와 고춧가루 검출률은 각각 73.3%, 91.5% 이었다. 고춧가루의 잔류농약 검출률이 건고추에 비해 다소 높게 나타났 다. 검출된 농약은 12종이었으며 모두 작물보호제 지침 서에 따른 고추에 사용가능한 살균제 및 살충제이었다. 가장 다빈도로 검출된 농약은 pyraclostrobin이었으며 다음으로 flubendiamide, azoxystrobin, chlorantraniliprole 순이었다. 검출된 농약에 대한 위해성을 ADI(Acceptable daily intake)대비 식이섭취율로 산출하여 평가한 결과, %ADI는 모두 5.66E-05 – 3.34E-02%로 나타나 안전한 것으로 나타났다.

본 연구에서는 농약의 음성시료에서는 acetylcholinesterase와 acetylthiocholine을 반응시켜 +전하와 -전하를 가지는 thiocholine으로 분해되어 금나노입자를 응집시켜 역 Y자 스트립상에서 청자색의 반응선(띠)을 형성하고 양성 시료에서는 생성시키지 않는 원리를 이용한 신속 농약 검출법을 개발 하였다. 개발한 분석법은 유기인계 농약 말라옥손과 카바메이트계 농약 카보퓨란을 각각 10 ng/mL 수준까지 검출이 가능한 것으로 확인되었으며, 2종의 유기인계와 카바메이트계 농약(EPN, dichlorvos)에 대해 추가적으로 검출 한계를 확인한 결과에서도 10 ng/mL 수준까지 모두 검출 가능함을 확인 할 수 있었다. 그러나 3종의 트리아진 계열의 농약과 각 1종의 피레스로이드, 카복사마이드, 페닐아마이드 및 유기염소 계열의 농약에 대해서는 반응성이 없는 것으로 확인되어 유기인계와 카바메이트계 농약 분석에 적용이 가능한 것으로 확인되었다. 마지막으로, 임의로 오염시킨 농산물 시료를 대상으로 분석법의 회수율을 확인한 결과, 말라옥손에 대해서 96.4에서100.7%, 카보퓨란은 81에서112.7%의 회수율이 확인되어 본 연구에서 개발한 역 Y자 스트립을 농약 검출법으로 이용한다면 농산물과 농업환경 중 존재하는 유기인계 및 카바메이트계 잔류농약을 신속하게 검출할 수 있을 것으로 판단된다.

본 연구에서는 농산물 시료 중 GC-NPD/MS 분석법을 이용하여 물리화학적 특성이 유사한 유기인계 살충제 chlorpyrifosmethyl, mecarbam, parathion-methyl, phenthoate, prothiofos, tebupirimfos, 유기인계 살균제 iprobenfos 및 유기인계 제초제 anilofos를 포함하는 8종의 유기인계 농약에 대해 동시 분석법을 확립하였다. 농산물 시료에 acetone을 가하여 추출된 대상 농약 8종의 잔류분은 n-hexane 분배법과 florisil 흡착 크로마토그래피법으로 정제하여 분석대상 시료로 하였다. DB-17 capillary column을 이용한 GC-NPD 분석 시 불순물의 간섭은 없었으며, 감귤, 고추, 배추, 현미 및 콩을 포함한 5종의 대표 농산물 중 대상농약 8종 각각의 정량한계(LOQ)는 tebupirimfos, chlorpyrifos-methyl 및 parathion-methyl은 0.004 mg/kg, 그 외 iprobenfos, mecarbam, prothiofos, phenthoate 및 anilofos는 0.008 mg/kg이었다. 5종의 대표 농산물에 대한 대상농약 전체의 회수율은 80.5~105.0%를 나타내었으며, 농산물 시료 및 처리수준에 관계없이 10% 미만의 분석오차를 나타내어 잔류분석기준 이내를 만족하였다. 본 연구에서 확립된 유기인계 농약 8종(anilofos, chlorpyrifos-methyl, iprobenfos, mecarbam, parathion-methyl, phenthoate, prothiofos 및 tebupirimfos)의 동시 분석법은 검출한계, 회수율 및 분 석오차 면에서 국제적 분석기준을 만족할 뿐만 아니라, GC/ MS SIM을 이용한 잔류분의 재확인 과정의 결과를 종합해 볼 때 분석과정의 편이성 및 신뢰성이 확보된 계열별 동시 분석법으로 국내·외 수출입 농산물 잔류농약 검사에 사용 가능할 것이다.

Pesticide application in agriculture provides significant benefits such as protection from disease, prevention of harmful insects, and increased crop yields. However, accurate toxicological tests and risk assessments are necessary because of many related adverse effects associated with pesticide use. In this review, we discuss and analyze residual pesticides contained in livestock feed in Korea. A pesticide residue tolerance standard for livestock feed has not been precisely established; so, risk assessments are required to ensure safety. Standards and approaches for animal criteria and appropriate methods for evaluating residual pesticides are discussed and analyzed based on technology related to animal product safety in Korea. The safety of livestock feed containing pesticides is assessed to establish maximum residue limits relative to pesticides. Analysis of residual pesticides in milk, muscle, brain, and fat was performed with a livestock residue test and safety evaluation of the detected pesticide was performed. Efficacy of organic solvent extraction and clean-up of feed was verified, and suitability of the instrument was examined to establish if they are effective, rapid, and safe. This review discussed extensively how pesticide residue tolerance in livestock feed and hazard evaluation may be applied in future studies.

본 연구는 딸기에서 발생하는 흰가루병 방제에 사용되는 살균제의 잔류시험을 수행하고 회귀방정 식 및 생물학적 반감기를 산출하여 한국과 일본, Codex의 잔류허용기준에 근거한 농약의 사용 및 안전한 농산물 생산에 기여하고자 수행되었다. 딸기재배 중 흰가루병 방제용 주요 살균제 boscalid, kresoxim-methyl, pyraclostrobin, pyrimethanil을 각 농약의 안전사용기준에 따라 기준량 1회 살포 후 1, 3, 5, 7, 9, 11, 13일에 딸기 시료를 채취하여 QuEChERS법을 이용하여 추출하고, NH2 SPE 카 트리지로 정제하여 HPLC/DAD로 분석하였다. 시험농약의 검출한계 및 정량한계는 4성분의 농약에서 모두 0.01과 0.03mg/kg이었으며, 평균회수율은 92.9~99.2%, 상대표준편차는≤5%로 산출되었다. 딸기 중 boscalid, kresoxim-methyl, pyraclostrobin, pyrimethanil의 생물학적 반감기는 기준량처리 시 각각 6.2, 4.0, 6.1, 6.6일로 나타났다. 이러한 결과로, 시설재배지 딸기 흰가루병 방제를 위해 사용되는 살균제의 안전 사용을 통해 국내 및 주요 수출국가의 MRL을 초과하지 않는 안전한 딸기를 생산하는데 기여할 것으로 기대된다.

The potential risk of heavy metals and residual pesticides in imported sawdust media inoculated with oak mushroom cultures is a concern for safe mushroom production in Korea. To obtain preliminary data for a sound analysis of this risk, this study was undertaken to analyze the presence of heavy metals and residual pesticides in the oak mushroom media imported from six different regions in China, between 2013 and 2015. Lead, arsenic, chrome, mercury, and cadmium were analyzed; arsenic, chrome, and mercury were not detected. Lead was detected in the imported oak mushroom media from Jinlin, Shandong, Liaoning, and Tianjin. The detection level of lead ranged from 1.7 to 3.2 mg/kg. Cadmium was detected at a level of 0.028 to 0.037 mg/kg in the media from Shandong and Liaoning. No residual pesticides were detected in any of the samples.

The Korean National Residue Program (KNRP) use three plans for the sampling of domestic meats: monitoring, surveillance, and exploratory testing. We analyzed the results of monitoring and surveillance for residual veterinary drugs and pesticides in meat during 2012 and 2013. KNRP targets food-producing animals including cattle, pigs, chickens, ducks, sheep (goats), and horses. Sampling mainly focuses on veterinary drugs and pesticide residues found in tissues such as muscle, kidney, and liver. A total of 548 residue violations occurred between 2012 and 2013, mainly in pigs (427 violations) and cattle (113 violations). The most commonly found compounds were antimicrobials such as penicillins, fluoroquinolones, aminoglycosides, tetracyclines, sulfonamides, and macrolides. Pig residue violations were mainly for the presence of penicillins (34%) and fluoroquinolones (28%), while most residue violations in cattle were due to the presence of penicillins (32%) and aminoglycosides (27%). The overall rates of violations were 0.21% in 2012 and 0.10% in 2013. A major cause of violations was the failure to follow the appropriate withdrawal periods (68.8%). The results of the KNRP were analyzed to provide information on agricultural chemical residues that are of public health concern and to help control and prevent residue violations for ensuring food safety.

The content of residual pesticides in commercial agricultural products in Gyeongsangbuk-Do area was investigated for 5 years extending the year 2004 through 2008. The detection rates of residual pesticides in agricultural products by year were similar in range of 11.6~16.4%. But the violation rates showed lower values in the last years from 4.5% of the year 2004 to 0% of the year 2007. The highest residual concentration of each pesticide detected in commercial agricultural products was investigated by year. That is, in the year 2004 and 2005, chlorpyrifos, chlorothalonil, diazinon, endosulfan, ethoprophos, fenarimol and procymidone were detected over the tolerance in kale, parsley, celery, chard and lettuce, and in the year 2006, permethrin in the soybean and peanut. The detection rate and violation rate of pesticides were highly increased in the order of the endosulfan, chlorpyrifos, procymidone, chlorfenapyr, fenitrothion, imazalil, isoprothiolane, methidathion and permethrin. The detection rate and violation rate of pesticides were increased after August every year.

For the development of integrated pest management system by harmonizing biological and chemical control, some experiments were carried out to select low toxic pesticides and to evaluate residual toxicity to natural enemies. Leaf dipping method and body dipping method were set up for evaluating toxicity to minute pirate bug, Orius strigicollis adult. We had tested 52 kinds of pesticides (33 insecticides, 19 fungicides) commonly used to control greenhouse insects, mites, and disease pests to natural enemies at the recommended concentration. Fourteen insecticides by body dipping method, 12 insecticides by leaf dipping method and 19 fungicides were selected as low toxic pesticides to O. strigicollis adult. After insecticide spraying at recommending dose on the sweet pepper plant, we examined residual effect of insecticides by introducing natural enemies on different days. Safety interval for introduction of O. strigicollis adult was established according to residual toxicity of pesticides. Safety insecticides at one day after treatment were pyraclofos, methomyl, thiodicarb, esfenvalerate bifenthrin, alpha-cypermethrin, etofenprox, fenvalerate, imidacloprid, acetamiprid, abamectin, emamectin benzoate, spinosad, indoxacarb. However, residual toxicity of neo-nicotinoids last up to 21 days to O. strigicollis adults.

For the development of integrated pest management system by harmonizing biological and chemical control, some experiments were carried out to select low toxic pesticides against natural enemies, and their residual toxicity were evaluated. Leaf dipping method, body dipping method, and diet treatment method were set up for the toxicity evaluation against Cotesia glomerata adults. We had tested 46 different pesticides (31 insecticides, 11 fungicides, 4 herbicides) at recommending concentration commonly used to control diamond back moth, disease and up-land weeds in chinese cabbage field. Twenty three insecticides, eleven fungicides, and four herbicides were shown to be low toxic to C. glomerata adults in the treatment of body dipping. After insecticide spraying at recommending dose on the chinese cabbage, we examined residual effect of insecticides by introducing natural enemies on different days. Safety interval for the introduction of C. glomerata adults was established according to the residual toxicity of pesticides. Safe insecticides for the introduction of C. glomerata adults at one day after treatment (DAT) were thiacloprid, acephate, chlorfenapyr, clothianidin and at 3 DAT were imidacloprid, deltamethrin, thiamethoxam, dimethylvinphos, emamectin benzoate.