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Development and Validation of a Simultaneous Analytical Method for 5 Residual Pesticides in Agricultural Products using GC-MS/MS (GC-MS/MS를 이용한 농산물 중 잔류농약 5종 동시시험법 개발 및 검증)

  • Park, Eun-Ji;Kim, Nam Young;Shim, Jae-Han;Lee, Jung Mi;Jung, Yong Hyun;Oh, Jae-Ho
    • Journal of Food Hygiene and Safety
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    • v.36 no.3
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    • pp.228-238
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    • 2021
  • The aim of this research was to develop a rapid and easy multi-residue method for determining dimethipin, omethoate, dimethipin, chlorfenvinphos and azinphos-methyl in agricultural products (hulled rice, potato, soybean, mandarin and green pepper). Samples were prepared using QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and analyzed using gas chromatography-tandem mass spectrometry (GC-MS/MS). Residual pesticides were extracted with 1% acetic acid in acetonitrile followed by addition of anhydrous magnesium sulfate (MgSO4) and anhydrous sodium acetate. The extracts were cleaned up using MgSO4, primary secondary amine (PSA) and octadecyl (C18). The linearity of the calibration curves, which waas excellent by matrix-matched standards, ranged from 0.005 mg/kg to 0.3 mg/kg and yielded the coefficients of determination (R2) ≥ 0.9934 for all analytes. Average recoveries spiked at three levels (0.01, 0.1, 0.5 mg/kg) and were in the range of 74.2-119.3%, while standard deviation values were less than 14.6%, which is below the Codex guideline (CODEX CAC/GL 40).

Monitoring of Residual Pesticides and Exposure Assessment of Olive Oil Products Sold on the Market (올리브유의 잔류농약 모니터링 및 노출량 조사)

  • Mi-Hui Son;Jae-Kwan Kim;You-Jin Lee;Ji-Eun Kim;Eun-Jin Baek;Byeong-Tae Kim;Seong-Nam Lee;Myoung-Ki Park;Yong-Bae Park
    • Journal of Food Hygiene and Safety
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    • v.38 no.4
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    • pp.211-216
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    • 2023
  • 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.

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.

A study of analytical method for Benzo[a]pyrene in edible oils (식용유지 중 벤조피렌 분석법 비교 연구)

  • Min-Jeong Kim;jun-Young Park;Min-Ju Kim;Eun-Young Jo;Mi-Young Park;Nan-Sook Han;Sook-Nam Hwang
    • Analytical Science and Technology
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    • v.36 no.6
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    • pp.291-299
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    • 2023
  • The benzo[a]pyrene in edible oils is extracted using methods such as Liquid-liquid, soxhlet and ultrasound-assisted extraction. However these extraction methods have significant drawbacks, such as long extraction time and large amount of solvent usage. To overcome these drawbacks, this study attempted to improve the current complex benzo[a]pyrene analysis method by applying the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method that can be analyzed in a simple and short time. The QuEChERS method applied in this study includes extraction of benzo[a]pyrene into n-hexane saturated acetonitrile and n-hexane. After extraction and distribution using magnesium sulfate and sodium chloride, benzo[a]pyrene is analyzed by liquid chromatography with fluorescence detector (LC/FLR). As a result of method validation of the new method, the limit of detection (LOD) and quantification (LOQ) were 0.02 ㎍/kg and 0.05 ㎍/kg, respectively. The calibration curves were constructed using five levels (0.1~10 ㎍/kg) and coefficient (R2) was above 0.99. Mean recovery ratio was ranged from 74.5 to 79.3 % with a relative standard deviation (RSD) between 0.52 to 1.58 %. The accuracy and precision were 72.6~79.4 % and 0.14~7.20 %, respectively. All results satisfied the criteria ranges requested in the Food Safety Evaluation Department guidelines (2016) and AOAC official method of analysis (2023). Therefore, the analysis method presented in this study was a relatively simple pretreatment method compared to the existing analysis method, which reduced the analysis time and solvent use to 92 % and 96 %, respectively.

Monitoring and Risk Assessment of Pesticide Residues in Herbal Medicines in Incheon (인천광역시 유통 한약재의 잔류농약 실태 조사 및 위해평가)

  • Min-jeong Kang;Sung-Hee Kwon;Sun-Hoi Kim;Mi-Sook Yeom;Byung-Kyu Park;Hee-jeong Lee;Ji-Hyeung Kim;Kwang-sig Joo;Myung-je Heo;Mun-ju Kwon
    • Journal of Food Hygiene and Safety
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    • v.39 no.2
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    • pp.118-127
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    • 2024
  • This study investigated the levels of 345 pesticide residues in 50 herbal medicines sold in Incheon metropolitan city to determine their safety. Pesticide residues are harmful substances that can cause serious health problems owing to their toxicity and carcinogenicity. The analysis of pesticide residues in the samples was conducted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method, known for its high analysis efficiency, to analyze a wide range of pesticides for which no standards have been set. The analysis was cross-validated with the pretreatment method outlined in the Korea Pharmacopoeia. Among the 50 samples encompassing 24 different herbs, 22 pesticide residues were detected in 24 samples, covering 7 distinct herbs, resulting in a detection rate of 48%. It is noteworthy that, except for two cases, all detected pesticides were those for which no standards were set. However, after conducting a risk evaluation considering the daily dosage of herb, it was determined that the levels of pesticide residues were within safe limits. Pesticides with high frequency within the same category of herbs were detected, indicating the necessity for continuous monitoring and regulation. In addition, comparative analysis using the pretreatment method outlined in the Korean Pharmacopoeia, yielded similar results, suggesting the possibility of analyzing pesticide residues in herbs using the QuEChERS method. The study emphasizes the importance of continuous monitoring of pesticide residues in herbs and the development of high-efficiency reliability analysis methods should continue to ensure consumer safety.

Monitoring of Pesticide Residues and Heavy Metals in Fermented Liquor in Ulsan (울산지역 유통 발효주의 잔류농약 및 중금속 실태조사)

  • Hee-Jung Kim;Kyoung-Jin Kim;Min-Kyung Kim;Geum-Bi Kim;Su-Hee Kim;Young-Kyung Jo;Ju-Eun Park;So-Yeon Jeong;Won-Dug Seo;Young-Sun Choi
    • Journal of Food Hygiene and Safety
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    • v.39 no.3
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    • pp.250-259
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    • 2024
  • In this study, we investigated in pesticide residues and heavy metals in fermented liquor products (wine, beer, makgeolli). Targeted analysis of 400 pesticide residues in the sample was performed using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction method, followed by gas chromatography-tandem mass spectrometry (MS/MS) and LC-MS/MS. The contents of heavy metals (Pb, Cd) were determined by ICP-MS using the microwave method. The mercury was measured using a mercury analyzer. From the analysis of 150 cases, 102 (68.0%) cases of fermented liquor were detected, and 35 pesticide residues (including metalaxyl, mandipropamid, azoxystrobin, and fenhexamid) were detected among the 400 pesticide residues tested. Pb, Cd, and Hg were tested in 150 samples. Lead was detected in 73 samples (48.7%), cadmium in 9 samples (6.0%), and mercury in 36 samples (24.0%). Exposure assessment was conducted to determine the safety of the detected pesticide residues and heavy metals. According to this assessment, the pesticide residues and heavy metals showed very low %ADI values (less than 1%).

A Comparative Study of Vegetation Phenology Using High-resolution Sentinel-2 Imagery and Topographically Corrected Vegetation Index (고해상도 Sentinel-2 위성 자료와 지형효과를 고려한 식생지수 기반의 산림 식생 생장패턴 비교)

  • Seungheon Yoo;Sungchan Jeong
    • Korean Journal of Agricultural and Forest Meteorology
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    • v.26 no.2
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    • pp.89-102
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    • 2024
  • Land Surface Phenology (LSP) plays a crucial role in understanding vegetation dynamics. The near-infrared reflectance of vegetation (NIRv) has been increasingly adopted in LSP studies, being recognized as a robust proxy for gross primary production (GPP). However, NIR v is sensitive to the terrain effects in mountainous areas due to artifacts in NIR reflectance cannot be canceled out. Because of this, estimating phenological metrics in mountainous regions have a substantial uncertainty, especially in the end of season (EOS). The topographically corrected NIRv (TCNIRv) employs the path length correction (PLC) method, which was deduced from the simplification of the radiative transfer equation, to alleviate limitations related to the terrain effects. TCNIRv has been demonstrated to estimate phenology metrics more accurately than NIRv, especially exhibiting improved estimation of EOS. As the topographic effect is significantly influenced by terrain properties such as slope and aspect, our study compared phenology metrics estimations between south-facing slopes (SFS) and north-facing slopes (NFS) using NIRv and TCNIRv in two distinct mountainous regions: Gwangneung Forest (GF) and Odaesan National Park (ONP), representing relatively flat and rugged areas, respectively. The results indicated that TCNIR v-derived EOS at NFS occurred later than that at SFS for both study sites (GF : DOY 266.8/268.3 at SFS/NFS; ONP : DOY 262.0/264.8 at SFS/NFS), in contrast to the results obtained with NIRv (GF : DOY 270.3/265.5 at SFS/NFS; ONP : DOY 265.0/261.8 at SFS/NFS). Additionally, the gap between SFS and NFS diminished after topographic correction (GF : DOY 270.3/265.5 at SFS/NFS; ONP : DOY 265.0/261.8 at SFS/NFS). We conclude that TCNIRv exhibits discrepancy with NIR v in EOS detection considering slope orientation. Our findings underscore the necessity of topographic correction in estimating photosynthetic phenology, considering slope orientation, especially in diverse terrain conditions.

Regional Development And Dam Construction in Korea (한국의 지역개발과 댐건설)

  • 안경모
    • Water for future
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    • v.9 no.1
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    • pp.38-42
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    • 1976
  • Because of differences in thoughts and ideology, our country, Korea has been deprived of national unity for some thirty years of time and tide. To achieve peaceful unification, the cultivation of national strength is of paramount importance. This national strength is also essential if Korea is to take rightful place in the international societies and to have the confidence of these societies. However, national strength can never be achieved in a short time. The fundamental elements in economic development that are directly conducive to the cultivation of national strength can be said to lie in -a stable political system, -exertion of powerful leadership, -cultivation of a spirit of diligence, self-help and cooperation, -modernization of human brain power, and -establishment of a scientific and well planned economic policy and strong enforcement of this policy. Our country, Korea, has attained brilliant economic development in the past 15 years under the strong leadership of president Park Chung Hee. However, there are still many problems to be solved. A few of them are: -housing and home problems, -increasing demand for employment, -increasing demand for staple food and -the need to improve international balance of payment. Solution of the above mentioned problems requires step by step scientific development of each sector and region of our contry. As a spearhead project in regional development, the Saemaul Campaign or new village movement can be cited. The campaign is now spreading throughout the country like a grass fire. However, such campaigns need considerable encouragement and support and the means for the desired development must be provided if the regional and sectoral development program is to sucdceed. The construction of large multipurpose dams in major river basin plays significant role in all aspects of national, regional and sectoral development. It ensures that the water resource, for which there is no substitute, is retained and utilized for irrigation of agricultural areas, production of power for industry, provision of water for domestic and industrial uses and control of river water. Water is the very essence of life and we must conserve and utilize what we have for the betterment of our peoples and their heir. The regional and social impact of construction of a large dam is enormous. It is intended to, and does, dras tically improve the "without-project" socio-economic conditions. A good example of this is the Soyanggang multipurpose dam. This project will significantly contribute to our national strength by utilizing the stored water for the benefit of human life and relief of flood and drought damages. Annual average precipitation in Korea is 1160mm, a comparatively abundant amount. The catchment areas of the Han River, Keum River, and Youngsan River are $62,755\textrm{km}^2$, accounting for 64% of the national total. Approximately 62% of the national population inhabits in this area, and 67% of the national gross product comes from the area. The annual population growth rate of the country is currently estimated at 1.7%, and every year the population growth in urban area increases at a rising rate. The population of Seoul, Pusan, and Taegu, the three major cities in Korea, is equal to one third of our national total. According to the census conducted on October 1, 1975, the population in the urban areas has increased by 384,000, whereas that in rural areas has decreased by 59,000,000 in the past five years. The composition of population between urban and rural areas varied from 41%~59% in 1959 to 48%~52% in 1975. To mitigate this treand towards concentration of population in urban areas, employment opportunities must be provided in regional and rural areas. However, heavy and chemical industries, which mitigate production and employment problems at the same time, must have abundant water and energy. Also increase in staple food production cannot be attained without water. At this point in time, when water demand is rapidly growing, it is essential for the country to provide as much a reservoir capacity as possible to capture the monsoon rainfall, which concentarated in the rainy seaon from June to Septesmber, and conserve the water for year round use. The floods, which at one time we called "the devil" have now become a source of immense benefit to Korea. Let me explain the topographic condition in Korea. In northern and eastern areas we have high mountains and rugged country. Our rivers originate in these mountains and flow in a general southerly or westerly direction throught ancient plains. These plains were formed by progressive deposition of sediments from the mountains and provide our country with large areas of fertile land, emminently suited to settlement and irrigated agricultural development. It is, therefore, quite natural that these areas should become the polar point for our regional development program. Hower, we are fortunate in that we have an additional area or areas, which can be used for agricultural production and settlement of our peoples, particularly those peoples who may be displaced by the formation of our reservoirs. I am speaking of the tidelands along the western and southern coasts. The other day the Ministry of Agriculture and Fishery informed the public of a tideland reclamation of which 400,000 hectares will be used for growing rice as part of our national food self-sufficiency programme. Now, again, we arrive at the need for water, as without it we cannot realize this ambitious programme. And again we need those dams to provide it. As I mentioned before, dams not only provide us with essential water for agriculture, domestic and industrial use, but provide us with electrical energy, as it is generally extremely economical to use the water being release for the former purposes to drive turbines and generators. At the present time we have 13 hydro-electric power plants with an installed capacity of 711,000 kilowatts equal to 16% of our national total. There are about 110 potential dams ites in the country, which could yield about 2,300,000 kilowatts of hydro-electric power. There are about 54 sites suitable for pumped storage which could produce a further 38,600,000 kilowatts of power. All available if we carefully develop our water resources. To summarize, water resource development is essential to the regional development program and the welfare of our people, it must proceed hand-in-hand with other aspects of regional development such as land impovement, high way extension, development of our forests, erosion control, and develop ment of heavy and chemical industries. Through the successful implementation of such an integrated regional development program, we can look forward to a period of national strength, and due recognition of our country by the worlds societies.

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Development and Validation of the Analytical Method for Oxytetracycline in Agricultural Products using QuEChERS and LC-MS/MS (QuEChERS법 및 LC-MS/MS를 이용한 농산물 중 Oxytetracycline의 잔류시험법 개발 및 검증)

  • Cho, Sung Min;Do, Jung-Ah;Lee, Han Sol;Park, Ji-Su;Shin, Hye-Sun;Jang, Dong Eun;Cho, Myong-Shik;Jung, ong-hyun;Lee, Kangbong
    • Journal of Food Hygiene and Safety
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    • v.34 no.3
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    • pp.227-234
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    • 2019
  • An analytical method was developed for the determination of oxytetracycline in agricultural products using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method by liquid chromatography-tandem mass spectrometry (LC-MS/MS). After the samples were extracted with methanol, the extracts were adjusted to pH 4 by formic acid and sodium chloride was added to remove water. Dispersive solid phase extraction (d-SPE) cleanup was carried out using $MgSO_4$ (anhydrous magnesium sulfate), PSA (primary secondary amine), $C_{18}$ (octadecyl) and GCB (graphitized carbon black). The analytes were quantified and confirmed with LC-MS/MS using ESI (electrospray ionization) in positive ion MRM (multiple reaction monitoring) mode. The matrix-matched calibration curves were constructed using six levels ($0.001{\sim}0.25{\mu}g/mL$) and coefficient of determination ($r^2$) was above 0.99. Recovery results at three concentrations (LOQ, $10{\times}LOQ$, and $50{\times}LOQ$, n=5) were from 80.0 to 108.2% with relative standard deviations (RSDs) less than of 11.4%. For inter-laboratory validation, the average recovery was in the range of 83.5~103.2% and the coefficient of variation (CV) was below 14.1%. All results satisfied the criteria ranges requested in the Codex guidelines (CAC/GL 40-1993, 2003) and the Food Safety Evaluation Department guidelines (2016). The proposed analytical method was accurate, effective and sensitive for oxytetracycline determination in agricultural commodities. This study could be useful for safety management of oxytetracycline residues in agricultural products.

Development of a Simultaneous Analytical Method for Determination of Insecticide Broflanilide and Its Metabolite Residues in Agricultural Products Using LC-MS/MS (LC-MS/MS를 이용한 농산물 중 살충제 Broflanilide 및 대사물질 동시시험법 개발)

  • Park, Ji-Su;Do, Jung-Ah;Lee, Han Sol;Park, Shin-min;Cho, Sung Min;Kim, Ji-Young;Shin, Hye-Sun;Jang, Dong Eun;Jung, Yong-hyun;Lee, Kangbong
    • Journal of Food Hygiene and Safety
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    • v.34 no.2
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    • pp.124-134
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    • 2019
  • An analytical method was developed for the determination of broflanilide and its metabolites in agricultural products. Sample preparation was conducted using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method and LC-MS/MS (liquid chromatograph-tandem mass spectrometer). The analytes were extracted with acetonitrile and cleaned up using d-SPE (dispersive solid phase extraction) sorbents such as anhydrous magnesium sulfate, primary secondary amine (PSA) and octadecyl ($C_{18}$). The limit of detection (LOD) and quantification (LOQ) were 0.004 and 0.01 mg/kg, respectively. The recovery results for broflanilide, DM-8007 and S(PFP-OH)-8007 ranged between 90.7 to 113.7%, 88.2 to 109.7% and 79.8 to 97.8% at different concentration levels (LOQ, 10LOQ, 50LOQ) with relative standard deviation (RSD) less than 8.8%. The inter-laboratory study recovery results for broflanilide and DM-8007 and S (PFP-OH)-8007 ranged between 86.3 to 109.1%, 87.8 to 109.7% and 78.8 to 102.1%, and RSD values were also below 21%. All values were consistent with the criteria ranges requested in the Codex guidelines (CAC/GL 40-1993, 2003) and the Food and Drug Safety Evaluation guidelines (2016). Therefore, the proposed analytical method was accurate, effective and sensitive for broflanilide determination in agricultural commodities.