Agricultural Product Samples Research Articles

Cascade Amplifying Electrochemical Bioanalysis for Zearalenone Detection in Agricultural Products: Utilizing a Glucose-Fenton-HQ System on Bimetallic-ZIF@CNP Nanocomposites.

The integration of advanced materials and signaling cascade strategies is a promising and highly relevant topic for enhancing the performance of bioanalysis. In this study, a three-stage cascade amplification electrochemical bioanalysis (TCAE-bioanalysis) was developed and evaluated for the detection of zearalenone (ZEN). This method couples immunoreaction with a glucose-Fenton-hydroquinone (HQ) system on bimetallic-ZIF (B-ZIF)@CNP nanocomposites. The B-ZIF@CNP-modified gold electrode (AuE) was prepared, offering high conductivity and an excellent reaction interface. The immunoreaction introduced glucose oxidase (GOx) into the glucose-Fenton-HQ system, generating an abundant electron signal. The method achieved an ultrasensitive limit of detection (LOD) as low as 0.87 pg/mL, with an IC50 value of 30.8 pg/mL, representing a 229-fold enhancement in sensitivity compared to ELISA using the same monoclonal antibody (McAb). The specificity, reliability, and practicality of this approach were thoroughly demonstrated for agricultural product samples. Additionally, the TCAE-bioanalysis offers several advantages, including simplified preparation for advanced B-ZIF@CNP, a convenient detection system, and the use of common and environmentally friendly reagents. This study presents a comprehensive approach to improving electrochemical bioanalysis and may also expand the application of signaling cascades and environmentally friendly techniques in other biosensing or diagnostic contexts.

Antimicrobial susceptibility in bacterial isolates from water and agricultural products of the Chanchán river, Chimborazo Province, Ecuador

Introduction: river contamination with pathogenic and multidrug-resistant microorganisms is a public health issue due to its impact on health and its potential to transmit infectious diseases. Objective: To determine the presence of multidrug-resistant bacteria in irrigation water samples and agricultural products from the Chachán River. Method: a descriptive, non-experimental study with a quantitative and cross-sectional approach was conducted. Water samples were collected from six different points, and pH and temperature were measured. Additionally, 13 agricultural product samples from the same points were analyzed. The identification and antimicrobial susceptibility testing of bacteria were performed using the VITEK2 system and amplification and sequencing of the 16S rRNA gene. Results: a total of 17 bacterial strains were isolated from the water samples, 16 of which (94 %) belonged to the order Enterobacterales, including Proteus mirabilis, Proteus vulgaris, Morganella morganii, and Citrobacter diversus. From the agricultural products, 24 bacteria were isolated, including species of Klebsiella, Stenotrophomonas maltophilia, and Enterococcus faecalis. Antimicrobial resistance was observed in various strains, notably P. mirabilis, C. diversus, and P. vulgaris with multiple resistances. Resistance was also identified in pathogenic strains such as Yersinia enterocolitica, Plesiomonas shigelloides, and Aeromonas hydrophila. Conclusions: the Chachan River and the agricultural products irrigated with its waters contain multidrug-resistant bacteria, posing a significant risk to public health. It is crucial to implement control and monitoring measures to reduce the spread of these pathogens and ensure food safety

A correction method for mitigating inter-instrumental absorbance drift in grating-based near-infrared spectrometers

In near-infrared spectroscopy analysis, the accuracy of instrument wavelength and breadth is crucial as it forms the foundation for transferring different instrument models. Wavelength and absorbance drift in grating-based scanning instruments result from differences in the grating, detector, and wavelength scanning system. Spectral wavelength drift can be corrected using materials such as polyethylene and polystyrene, which have absorption peaks in the near-infrared region. To reduce absorbance drift in spectra at different wavelength points, this article proposes a point-by-point linear correction method for near-infrared spectra using a small number of typical agricultural product samples. The method constructs a linear relationship model for the absorbance of each wavelength point between the main instrument and slave instruments. The study used seven S450 grating-based diffuse reflection near-infrared spectroscopy instruments, one serving as the main instrument and the remaining six as slave instruments. The point-by-point linear correction method was used to correct wheat spectra collected by the slave instruments, and a crude protein content model for wheat was established for prediction. The results showed that the method reduces spectral differences between different instruments, improves spectral consistency, and reduces prediction errors, achieving better model sharing between instruments. After correcting, the average normalized variation coefficient of wheat spectra decreased by 95.12%, from 7.78% to 0.38%, and the average standard deviation of the predicted results decreased by 78.18%, from 0.5321 to 0.1161. The correction effect of the method combined with traditional pre-processing methods was better than using pre-processing methods alone. Overall, the point-by-point correction method based on a small number of typical agricultural product samples has a significant effect on improving the accuracy of near-infrared spectroscopy analysis.

Magnetic three-phase single-drop microextraction for highly sensitive detection of aflatoxin B1 in agricultural product samples based on peroxidase-like spatial network structure.

In this work, a highly sensitive method for aflatoxin B1 (AFB1) detection was developed based on a peroxidase-like spatial network structure. The specific antibody and antigen of AFB1 were coated on a histidine-modified Fe3O4 nanozyme to form the capture/detection probes. Based on the competition/affinity effect, the spatial network structure was constructed by the probes, which could be rapidly (8s) separated by a magnetic three-phase single-drop microextraction process. In this single-drop microreactor, the network structure was applied to catalyze a colorimetric 3,3',5,5'-tetramethylbenzidine oxidation reaction for AFB1 detection. The signal was amplified significantly due to the strong peroxidase-like ability of the spatial network structure and the enrichment effect of the microextraction. Thus, a low detection limit (0.034pg/mL) was achieved. The matrix effect of real sample can be eliminated by the extraction approach, and the practicability of this method was proved by agricultural product samples analysis.

A Turn-On Fluorescence Sensor Based on Nitrogen-Doped Carbon Dots and Cu2+ for Sensitively and Selectively Sensing Glyphosate

Glyphosate has excellent herbicidal activity, and its extensive use may induce residue in the environment and enter into humans living through the food chain, causing negative impact. Here, water-soluble 1.55 nm size nitrogen-doped carbon quantum dots (NCDs) with strong blue fluorescence were synthesized using sodium citrate and adenine. The maximum excitation and emission wavelengths of NCDs were 380 nm and 440 nm, respectively. The above synthesized NCDs were first used for the construction of a fluorescence sensor for glyphosate detection. It was found that Cu2+ could quench the fluorescence of NCDs effectively through the photoinduced electron transfer (PET) process, which was confirmed using fluorescence lifetime measurements. Additionally, the fluorescence was restored with the addition of glyphosate. Hence, a sensitive turn-on fluorescence sensor based on NCDs/Cu2+ for glyphosate analysis was developed. The LODs of glyphosate for water and rice samples were recorded as 0.021 μg/mL and 0.049 μg/mL, respectively. The sensor was applied successfully for ultrasensitive and selective detection of glyphosate in environmental water and rice samples with satisfied recoveries from 82.1% to 113.0% using a simple sample pretreatment technique. The proposed strategy can provide a significant potential for monitoring glyphosate residue in water and agricultural product samples.

Characteristics of Antimony Migration and Transformation and Pollution Evaluation in a Soil-Crop System Around a Tin Mine in Hunan Province

This study used 193 sets of farmland soil and agricultural product samples collected from around a tin mine in Hunan Province, China, to explore the antimony (Sb) content characteristics and pollution status of soil and agricultural products and to provide a scientific basis for the prevention and control of soil antimony pollution in antimony mining areas and the safe use of farmland. We analyzed the amount of antimony in the soil, basic physical and chemical properties, and antimony content in agricultural products; studied the characteristics of antimony migration and transformation in the soil-agricultural product system; and conducted safety assessments on soil and agricultural products. The results showed that the soil ω(Sb) in the central area of the mine, the southern area of the mine, the central township area, the urban-rural transfer area, and the northern area of the mine reached (2348±2165), (1298±884.1), (311.8±526.5), (302.5±355.9), and (215.6±183.2) mg·kg-1, and the exceeding multiples reached 65.22, 36.06, 8.66, 8.40, and 5.99 times, respectively. The antimony enrichment coefficients of lettuce, scallion, cabbage, water spinach, garlic, and pea seedlings in agricultural products were 0.01-0.1, which indicated good antimony absorption capacity. The antimony enrichment coefficients of loofah, asparagus lettuce, pepper, carrot, bitter gourd, corn, eggplant, cowpea, and celery were less than 0.01, and the antimony absorption capacity was relatively poor. The safety assessment results showed that roots, allium, and garlic vegetables had a high risk of antimony pollution; leafy vegetables and legumes had a higher risk of antimony pollution; and solanaceous vegetables, melons, and fruit vegetables and corn (cereals) had a high risk of antimony pollution. Therefore, it is urgent to take soil antimony pollution control measures in the mining area. At the same time, in order to realize the safe use of agricultural land in the mining area, the farmland far away from the low antimony content of the soil in the central area of the mine should be selected as the planting area, and the agricultural products with weak antimony absorption capacity should be planted first.

Perfluorinated compounds in a river basin from QingHai-Tibet Plateau: Occurrence, sources and key factors

The occurrence of perfluorinated compounds (PFCs) in different environmental media in the QingHai-Tibet Plateau has been limitedly investigated. In this study, the water, sediments, soils and agricultural product samples were collected in the Huangshui River basin, and contents of the PFCs and values of water parameters were determined. This study investigated dominantly regulating factors of the distribution of PFCs in the water emphatically, explored the sources and assessed potential risks of the PFCs integrally. The results showed that perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluorobutanoic acid (PFBA) and perfluorooctanoic acid presented high maximum concentrations of 3207.42, 3015.96, 1941.89 and 826.4 ng L−1 in the water, respectively. There were 12 PFCs detected in crops, with the maximum concentration of 5206.86 ng g−1 for PFBA. The significantly positive correlation (p < 0.05) was observed between the concentrations of PFBA in crops and that in adjacent rivers, indicating that the irrigation most likely contributed to the accumulation of PFBA in the studied crops. The occurrence of the PFCs in the water during the dry season was dominantly regulated by fluorescent dissolved organic matters via the hydrophobic interaction, while it was primarily regulated by the total nitrogen and electrical conductivity via electrostatic interaction during the wet season. The PFCs in the water were mainly from the wastewater discharged from wastewater treatment plants and carpet factories, while the resuspension of the PFCs in sediments was also an important contribution especially in wet season. The PFCs in the river has posed sustained risk to the public health, especially children.

Magnetic Solid-Phase Extraction Based on Amino-functionalized Magnetic Starch for Analysis of Organochlorine Pesticides.

A magnetic starch modified with 3,5-diaminobenzoic acid and 3-aminopropyltriethoxysilane (Fe-starch@DABA-APTES) was synthesized and applied as adsorbent for the extraction of organochlorine pesticides (OCPs). Magnetic solid-phase extraction was developed using 75 mg of the sorbent and 15 mL of a sample solution. Extraction was conducted on a vortex mixer for 40 s. The adsorbent was collected using an external magnet before eluting the analytes using 0.5 mL of methanol. Quantification of the analytes was performed using gas chromatography with a micro-electron capture detector. The linearity was obtained for the studied OCPs in the range between 0.01 - 2.00 μg L-1. The detection and quantification limits were obtained in ranges of 0.5 - 4.0 and 1.5 - 15.0 ng L-1, respectively, with enrichment factors of up to 39. The precision in terms of the intra- and inter-day relative standard deviations (RSDs) were below 4.75, and 9.25%, respectively. The developed method has been applied in natural water and agricultural product samples. The recoveries ranged between 59.83 - 132.67% (RSDs < 10.73%).

Pesticide Analysis in Agricultural Products by GC-MS/MS Using STQ Method

As a method to detect pesticide residues in agricultural products, we evaluated the pretreatment of agricultural product samples by the solid-phase extracton technique with QuEChERS (STQ) method followed by GC-MS/MS with large-volume injection using a stomach-type glass-lined injector. This method satisfied the target criteria of recovery (70-120%) and the standard deviation of repeatability (RSD<25%) in 238-282 pesticides found in six types of agricultural products.

Contamination by As, Hg, and Sb in a region with geogenic As anomaly and subsequent human health risk characterization.

Arsenic (As) is among the most harmful toxic elements to human health with severe carcinogenic and non-carcinogenic effects. The present study aims to (1) characterize a site with geogenic As anomaly (Emet basin) in Kutahya, Turkey via soil (urban, agriculture, forest; n = 53 total), water (n = 11), and agricultural product (n = 19) samples; and, (2) characterize human health risks for different receptors under specific exposure scenarios. Soil As levels were very high (range, 22.4-765mgkg-1). Previous literature suggested some evidence of Sb and Hg combined with As in mineral forms in the region; the present study found elevated Sb (up to 76.0mgkg-1) in two regions with very high As levels, but Hg concentrations were low in the region. Soils from urban/agricultural zones (representing anthropogenic impact) did not have statistically different As levels compared with forest soils (representing low/no human impact). As water concentrations were also very high (range, 14.0-729μgL-1), however, uptake by agricultural products was low, mostly limited to wheat (up to 0.7mgkg-1). Exposure assessment/risk characterization showed that non-carcinogenic risk following exposure to soils was very high for children (hazard index up to 37 under reasonable maximum exposure) as well as carcinogenic risk (probability up to 1.19E-3). The risk was even higher considering intake of water, and in this case, both for children and adults (HI, 4.0-66.6; cancer risk, 1.29E-4-1.84E-2). The potential adverse outcomes of the As anomaly in the region may be grave, thus further geochemical investigation of As speciation and mobile fractions as well as gastrointestinal As bioaccessibility supplementing probabilistic human health risk characterization are recommended.

Survey of Deoxynivalenol Contamination in Agricultural Products in the Chinese Market Using An ELISA Kit.

A total of 328 agricultural product samples highly suspected to be contaminated, from flour companies, feed companies, and livestock farms throughout China, were surveyed for deoxynivalenol (DON) contamination using a self-assembly enzyme-linked immunosorbent assay (ELISA) kit. An ELISA kit for DON was developed with a 4.9 ng mL−1 limit of detection (LOD) in working buffer and a 200 ng g−1 LOD in authentic samples. The DON contamination detection rate was 88.7%, concentrations ranged from 200.9 to 6480.6 ng g−1, and the highest DON contamination was found in distillers’ dried grains with solubles with an average of 3204.5 ng g−1. Wheat bran and wheat were found to be the most commonly contaminated samples, and the corn meal samples had the lowest average DON level. This ELISA kit is a powerful alternative method for the rapid, sensitive, specific, accurate, and high-throughput determination of DON and can meet the maximum requirement levels. This survey suggests that DON contamination in the Chinese market is serious, and the contamination risk deserves attention. Essential preventive measures should be implemented to ensure food safety and human health.

Determination of residual organophosphorus thioester pesticides in agricultural products by chemical isotope-labelling liquid chromatography-tandem mass spectrometry coupled with in-syringe dispersive solid phase clean-up and in situ cleavage

Chemical isotope labelling in combination with high-performance liquid chromatography-tandem mass spectrometry (CIL-HPLC-MS/MS) is a powerful method for quantitative profiling of targeted molecules. In the current work, we successfully developed a novel CIL-HPLC-MS/MS method for quantitative profiling of residual organophosphorus thioester pesticides (OPTPs) in agricultural products through the determination of the cleavage products of thiol (CP-thiol) compounds. In this method, we synthesized a novel pair of CIL reagents, i.e., N-(4-(carbazole-9-yl)-phenyl)-N-maleimide (NCPM-d0) and its deuterated analogue NCPM-d2, both of which contain a maleimide moiety as the reactive group and an isotope tag to sensitively label CP-thiol compounds. NCPM-d0 was used to label CP-thiol compounds cleaved from OPTPs in the investigated agricultural product samples, and NCPM-d2 was used to label CP-thiol compounds cleaved from OPTPs in the standard substance-spiked organic agricultural product samples. The heavily labelled derivatives were used as the internal standards (ISs) to compensate for the matrix effects during MS analysis. The NCPM-d0- and NCPM-d2-labelled derivatives generated two characteristic product ions (PIs) at m/z 372.5 and 374.5 under collision induced dissociation, respectively, which are used to establish the multiple reaction monitoring (MRM) mode-based detection. The precursor ions of NCPM-d0 and NCPM-d2 labelled derivatives of CP-thiol compounds were deduced according to the structures of the OPTPs. The peak pairs with a fixed mass difference and similar retention times were assigned as potential CP-thiol candidates for the identification of the corresponding OPTPs. Using the proposed method, we successfully determined seven residual OPTPs in agricultural product samples. Taken together, the presented method was demonstrated to be a promising new technique in the quantitation of OPTPs in agricultural product samples with high reliability.

Rapid and Direct Microextraction of Pesticide Residues from Rice and Vegetable Samples by Supramolecular Solvent in Combination with Chemometrical Data Processing

In this work, a rapid, simple, and environmentally friendly method has been proposed for direct supramolecular microextraction of four organophosphate insecticides (ethion, phosalone, diazinon, chlorpyrifos) and an isothiazolidine acaricide (hexythiazox) in agricultural product samples prior to their determination by high-performance liquid chromatography-ultraviolet spectroscopy. These five target pesticides have been selected as models in combination with chemometrical optimization processing due to their high consumption in rice, cucumber, and tomato samples for pest control. Method is based on the extraction of pesticide residues from homogenized food sample in an aqueous media containing some tetrahydrofuran (THF) and decanoic acid (DeA). Effects of the experimental parameters, including THF volume, DeA content, salt concentration (as a measure of salting-out effect), and pH on extraction recoveries (ERs) and enrichment factors (EFs) were investigated and, then, the significant variables were optimized using central composite design (CCD) as chemometrical processing. At optimum conditions, this method has a linear response over the ranges of 0.10 to 1500 μg kg−1 for target analytes. Limits of detection (LOD) of this method were found to be in the range of 0.05 to 0.20 μg kg−1. Also, relative standard deviation (RSD) of the method was in the range of 3.45 to 12.27% and the enrichment factors ranged from 102- to 178-fold. The method was applied successfully for analysis of the pesticides in agricultural product samples.

Analysis of pyrethroid pesticides in Chinese vegetables and fruits by GC–MS/MS

A rapid and economical method using modified QuEChERS sample pretreatment coupled with high-sensitivity gas chromatography/triple quadrupole mass spectrometry was established to simultaneously determine ten pyrethroid pesticides in fruits and vegetables. All pesticides were detected within 20 min of one injection. Concurrent backflushing provided column protection, greatly facilitating instrument maintenance. For quantitation, matrix-matched calibration was used to compensate for signal-enhancement effects and to ensure the precision of the method. The limit of detection (LOD) was in the range of 0.3–4.9 μg/kg. The recovery rate was from 78.8 to 118.6%, with relative standard deviation (RSD) below 14.8%. The developed method is suitable for rapid and sensitive multi-residue analysis of pyrethroid pesticides in fruits and vegetables. It is good for users in professional institutions that implement safety controls for testing hundreds of agricultural product samples everyday.

Perfluorinated Compounds in Greenhouse and Open Agricultural Producing Areas of Three Provinces of China: Levels, Sources and Risk Assessment.

Field investigations on perfluoroalkyl acid (PFAA) levels in various environmental matrixes were reported, but there is still a lack of PFAA level data for agricultural environments, especially agricultural producing areas, so we collected soil, irrigation water and agricultural product samples from agricultural producing areas in the provinces of Liaoning, Shandong and Sichuan in China. The background pollution from instruments was removed and C4–C18 PFAAs were detected by LC-MS/MS. The concentrations of PFAAs in the top and deep layers of soil were compared, and the levels of PFAAs in different agricultural environments (greenhouses and open agriculture) were analyzed. We found the order of PFAA levels by province was Shandong > Liaoning > Sichuan. A descending trend of PFAA levels from top to deep soil and open to greenhouse agriculture was shown and perfluorobutanoic acid (PFBA) was considered as a marker for source analysis. Bean vegetables contribute highly to the overall PFAA load in vegetables. A significant correlation was shown between irrigation water and agricultural products. The EDI (estimated daily intake) from vegetables should be of concern in China.

Selection and application of broad-specificity human domain antibody for simultaneous detection of Bt Cry toxins

Bt Cry toxin is a kind of bio-toxins that used for genetically modified crops (GMC) transformation widely. In this study, total 15 positive clones could bind the Bt Cry toxins which isolated from a human domain antibody library by 5 rounds affinity selection. According to analyzing of PCR amplification and enzyme-linked immunosorbent assay (ELISA), the most positive phage domain antibody (named F5) gene was cloned into the pET26b vector and expressed in E. coli BL21. The purified antibody was used to develop an indirect competitive ELISA (IC-ELISA) for Cry1Ab, Cry1Ac, Cry1B, Cry1C and Cry1F toxins, respectively. The working range of detection for standard curves in IC-ELISA were 0.258–1.407 μg/mL, the medium inhibition concentration (IC50) were 0.727–0.892 μg/mL and detection limit (IC10) were 0.029–0.074 μg/mL for those Bt Cry toxins. The affinity of F5 domain antibody with Cry1Ab, Cry1Ac, Cry1B, Cry1C and Cry1F toxins were 1.21–5.94 × 107 M−1. The average recoveries of the 5 kinds of Bt Cry toxins from spiked wheat samples were ranged from 81.2%–100.8% with a CV at 2.5%–9.4%. The results showed that we successfully obtained the broad-specificity human domain antibody for simultaneous detection of Bt Cry toxins in agricultural product samples.

Determination for multiple mycotoxins in agricultural products using HPLC-MS/MS via a multiple antibody immunoaffinity column.

Mycotoxins usually found in agricultural products such as peanut, corn, and wheat, are a serious threat to human health and their detection requires multiplexed and sensitive analysis methods. Herein, a simultaneous determination for aflatoxin B1, B2, G1, G2, ochratoxin A, zearalanone and T-2 toxin was investigated using high performance liquid chromatography coupled with tandem mass spectrometry in a single run via a home-made multiple immunoaffinity column. Four monoclonal antibodies were produced in our lab against aflatoxins, ochratoxin A, zearalanone and T-2 toxin, respectively, then combined as a pool and bound to Sepharose-4B for affinity chromatography. Seven mycotoxins were effectively extracted from the agricultural product samples by using acetonitrile/water/acetic acid (80:19:1, v/v/v) Then, the extraction was cleanup by multiple immunoaffinity column. This method demonstrated a considerable linear range of 0.30-25, 0.12-20, 0.30-20, 0.12-20, 0.60-30, 0.30-25, and 1.2-40μgkg(-1)and lower limits of detection at 0.1, 0.04, 0.1, 0.04, 0.2, 0.1 and 0.4μgkg(-1) for AFB1, AFB2, AFG1, AFG2, OTA, ZEN and T-2, respectively, in comparison with previously reported methods, as well as excellent recoveries. The mIAC capacity for AFB1, AFB2, AFG1, AFG2, OTA, ZEN, and T-2 were 187, 181, 153, 151, 105, 130, 88ng, respectively. It was found that all of the 7 mycotoxins were present in 90 agricultural product samples. The proposed method meets the requirements for rapid sample preparation and highly sensitive identification of multiple mycotoxins in agricultural product and food safety. This method provides a promising alternative with high throughput and high sensitivity for rapid analysis of seven mycotoxins in the monitoring of food safety.

Development and validation of an analytical method for quantification of sulfuryl fluoride residues in agricultural products using gas chromatography with electron capture detection

Sulfuryl fluoride (SF) is used as a broad-spectrum fumigant due to toxicity against target pests, good dispersion, and a good penetrating ability. An analytical method for SF quantification in agricultural products was developed and validated to ensure food safety. SF residues were extracted from agricultural product samples using water in an airtight blender jar. Subsequently, an aliquot of the headspace was analyzed using capillary GC with an electron capture detector. Results were confirmed using GC-MS. The linear range of SF was 0.01–1.0 μg/mL with a correlation coefficient (r 2) of 0.999. Average SF recovery values ranged from 74.1 to 108.9% from spiked levels of 0.04–2.0 mg/kg, and the relative standard deviation was 0.5–6.8%. The limit of detection and the limit of quantification were 0.01 and 0.04 mg/L, respectively.

HPLC-UVD를 이용한 살균제 fenpyrazamine의 시험법 개발 및 검증

Pyrazole계 살균제 fenpyrazamine은 복숭아 (2.0 mg/kg), 포도 (5.0 mg/kg) 및 감귤 (2.0 mg/kg)에 잔류허용기준이 설정된 신규농약으로 농산물 중 fenpyrazamine 잔류량을 측정하기 위해 고성능 액체크로마토그래프를 이용한 정확하고 신뢰성 있는 효율적인 공정 시험법을 확립하고자 하였다. 추출용매는 acetonitrile로 선정하였으며, 액-액 분배 단계에서 dichloromethane과 물의 분배로 극성불순물을 제거하였고, 정제단계에서는 silica cartridge를 이용하여 hexane/acetone 용매 조성으로 다양한 매트릭스 간섭 물질로부터 fenpyrazamine을 효과적으로 정제할 수 있었다. 확립된 시험법으로 7종의 대표농산물[과일류 (복숭아, 포도, 감귤), 채소류 (고추), 서류 (감자), 콩류 (대두), 곡류 (현미)]에 처리농도 0.05, 0.5, 5.0 mg/kg으로 각각 5 반복의 회수율 실험을 시행한 결과 회수율 범위가 71.8~102.7%이었고, 분석오차가 10% 미만으로 시험법의 정확성을 확인하였으며, LC-MS를 통한 재확인 과정을 수행함으로써 시험법의 신뢰성과 선택성을 확보할 수 있었다. 따라서 본 연구에서 개발한 시험법은 농산물에 잔류하는 fenpyrazamine을 분석하기 위한 공정 시험법으로 활용할 수 있을 것으로 판단된다. Fenpyrazamine which is a pyrazole fungicide class for controlling gray mold, sclerotinia rot, and Monilinia in grapevines, stone fruit trees, and vegetables has been registered in republic of Korea in 2013 and the maximum residue limits of fenpyrazamine is set to grape, peach, and mandarin as 5.0, 2.0, and 2.0 mg/kg, respectively. Very reliable and sensitive analytical method for determination of fenpyrazamine residues is required for ensuring the food safety in agricultural products. Fenpyrazamine residues in samples were extracted with acetonitrile, partitioned with dichloromethane, and then purified with silica-SPE cartridge and eluted with hexane and acetone mixture. The purified samples were determined by HPLC-UVD and confirmed with LC-MS and quantified using external standard method. Linear range of fenpyrazamine was between <TEX>$0.1{\sim}5.0{\mu}g/mL$</TEX> with the correlation coefficient (r) 0.999. The average recovery ranged from 71.8 to 102.7% at the spiked level of 0.05, 0.5, and 5.0 mg/kg, while the relative standard deviation was between 0.1 and 7.3%. In addition, limit of detection and limit of quantitation were 0.01 and 0.05 mg/L, respectively. The results revealed that the developed and validated analytical method is possible for fenpyrazamine determination in agricultural product samples and will be used as an official analytical method.

국내 유통 과실류의 잔류농약 모니터링 및 위해성 평가

BACKGROUND: This study was conducted to monitor residual pesticides in domestic agricultural products and to assess their risk to human health. METHODS AND RESULTS: 123 samples containing both general and environment-friendly certified agricultural products were purchased from traditional domestic markets and supermarkets in six provinces of Korea. Multiresidue analyses of one hundred twenty-two pesticides except for herbicides were performed with gas chromatography-electron capture detector, gas chromatography-nitrogen/phosphorus detector, and high-performance liquid chromatography. Sixteen pesticides were detected in 45 agricultural product samples, which were 38 general, 6 low pesticide and 1 of GAP agricultural product samples and the detection rate was 33.6%. Pesticides detected in agricultural product samples were cypermethrin, lufenuron, fenvalerate, bifenthrin, chlorfenapyr and iprodione. Residual concentration of 18 samples were exceeded the recommended maximum residue limit set by Ministry of Food and Drug Safety and two kinds of unregistered pesticides in korea were also detected in two samples. CONCLUSION(S): In order to do risk assessment by agricultural products consumption, estimated daily intake of residual pesticides were determined and compared to acceptable daily intake, referring to %ADI values. The range of %ADI values was from 0.038% to 2.748%. Taken together, it demonstrates the pesticides found in agricultural products samples were below the safety margin, indicating no effect on human health.