Research

16 pages, 7464 KiB

Open AccessArticle

Development of Simultaneous Determination Method of Pesticide High Toxic Metabolite 3,4-Dichloroaniline and 3,5 Dichloroaniline in Chives Using HPLC-MS/MS

by Yibo Dong, Xiaolong Yao, Wanping Zhang and Xiaomao Wu

Foods 2023, 12(15), 2875; https://0-doi-org.brum.beds.ac.uk/10.3390/foods12152875 - 28 Jul 2023

Cited by 2 | Viewed by 915

Abstract

3,4-dichloroaniline (3,4-DCA) and 3,5-dichloroaniline (3,5-DCA) are, respectively, the primary metabolites deriving from the breakdown of phenylurea herbicides and dicarboximide fungicides in both soils and plants, whose residues in vegetable products have a heightened concern considering their higher health risks to humans and greater [...] Read more.

3,4-dichloroaniline (3,4-DCA) and 3,5-dichloroaniline (3,5-DCA) are, respectively, the primary metabolites deriving from the breakdown of phenylurea herbicides and dicarboximide fungicides in both soils and plants, whose residues in vegetable products have a heightened concern considering their higher health risks to humans and greater toxicity than the parent compounds in the environment. In this study, a sensitive high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was developed for the simultaneous determination of 3,4-DCA and 3,5-DCA residues in chive products based on the optimization of HPLC-MS/MS chromatographic and mass-spectrometric conditions using the standard substances and the modified QuEChERS preparation technique. The preparation efficiency of 3,4-DCA and 3,5-DCA from chive samples showed that acetonitrile was the best extractant. The combination of the purification agent graphite carbon black + primary secondary amine and the eluting agent acetonitrile + toluene (4:1, v/v) had a satisfactory purification effect. The linear correlation coefficients (R²) were more than 0.996 with the six concentration range of 0.001–1.000 mg/L for 3,4-DCA and 3,5-DCA. The limit of detection and limit of quantitation of this method was 0.6 and 2.0 µg/kg for 3,4-DCA, as well as 1.0 and 3.0 µg/kg for 3,5-DCA, respectively. The matrix effect range of 3,4-DCA and 3,5-DCA in chive tissues was from −9.0% to −2.6% and from −4.4% to 2.3%, respectively. The fortified recovery of 3,4-DCA and 3,5-DCA in chive samples at four spiked levels of 0.001–1.000 mg/kg was 75.3–86.0% and 78.2–98.1%, with the relative standard deviation of 2.1–8.5% and 1.4–11.9%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) of the method were 0.6, 2.0, and 1.0, 3.03 for 4-DCA and 3,5-DCA, respectively. This study highlights that the analytical method established here can efficiently and sensitively detect residues of 3,4-DCA and 3,5-DCA residues for monitoring chive products. The method was successfully applied to 60 batches of actual vegetable samples from different regions. Full article

(This article belongs to the Special Issue Rapid Analytical, Removal and Transformation of Chemical Residues in Foods)

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15 pages, 1722 KiB

Open AccessArticle

LC-MS/MS Method Minimizing Matrix Effect for the Analysis of Bifenthrin and Butachlor in Chinese Chives and Its Application for Residual Study

by So-Hee Kim, Yoon-Hee Lee, Mun-Ju Jeong, Da-Yeong Gwon, Ji-Ho Lee, Yongho Shin and Hoon Choi

Foods 2023, 12(8), 1683; https://0-doi-org.brum.beds.ac.uk/10.3390/foods12081683 - 18 Apr 2023

Cited by 7 | Viewed by 1779

Abstract

The matrix effect refers to the change in the analytical signal caused by the matrix in which the sample is contained, as well as the impurities that are co-eluted with the target analyte. In crop sample analysis using LC–MS/MS, the matrix effect can [...] Read more.

The matrix effect refers to the change in the analytical signal caused by the matrix in which the sample is contained, as well as the impurities that are co-eluted with the target analyte. In crop sample analysis using LC–MS/MS, the matrix effect can affect the quantification results. Chinese chives are likely to exhibit a strong matrix effect when co-extracted with bifenthrin and butachlor due to the presence of phytochemicals and chlorophyll. A novel analytical method was developed to reduce the matrix effects of bifenthrin and butachlor to a negligible level in Chinese chives. The established method had a limit of quantitation of 0.005 mg/kg and correlation coefficients greater than 0.999 within the range of 0.005–0.5 mg/kg. Matrix effects were found to be negligible, with values ranging from −18.8% to 7.2% in four different sources of chives and two leafy vegetables. Compared to conventional analytical methods for the LOQ and matrix effect, the established method demonstrated improved performances. The analytical method was further applied in a residual study in chive fields. The active ingredient of butachlor 5 granule (GR) was not detected after soil admixture application, while that of bifenthrin 1 emulsifiable concentrate (EC) showed a range from 1.002 to 0.087 mg/kg after foliar spraying. The dissipation rate constant (k) of bifenthrin was determined to be 0.115, thus its half-life was calculated to be 6.0 days. From the results, PHI and safety use standards of both pesticides were suggested. The developed analytical method can be applied to accurately determine bifenthrin and butachlor residues in Chinese chives and provides a foundation for further research on the fate and behavior of these pesticides in the environment. Full article

(This article belongs to the Special Issue Rapid Analytical, Removal and Transformation of Chemical Residues in Foods)

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15 pages, 1487 KiB

Open AccessArticle

Fungicide Dissipation Kinetics and Dietary Exposure Risk Assessment in Squash Fruit and Leaf

by Dai An, Rakdo Ko, Jinchan Kim, Kwanghun Lee and Ji-Ho Lee

Foods 2023, 12(6), 1291; https://0-doi-org.brum.beds.ac.uk/10.3390/foods12061291 - 17 Mar 2023

Cited by 2 | Viewed by 1206

Abstract

The dissipation behavior and dietary exposure risk assessment of four fungicides (dimethomorph, mandipropamid, myclobutanil, and metalaxyl) was performed in fruits and leaves of squash grown under greenhouse conditions. Squash fruit and leaf samples were randomly collected at 0, 3, 5, 7, and 14 [...] Read more.

The dissipation behavior and dietary exposure risk assessment of four fungicides (dimethomorph, mandipropamid, myclobutanil, and metalaxyl) was performed in fruits and leaves of squash grown under greenhouse conditions. Squash fruit and leaf samples were randomly collected at 0, 3, 5, 7, and 14 days after the last pesticide application. Analysis was performed using ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was used for sample preparation. Recovery rates at two spiked levels (0.01 and 0.1 mg/kg) were found to be in the range of 76.4%–101.9% for the analyzed pesticides and their relative standard deviations were ≤4%. Pesticide half-lives were 2.1 and 4.9 days for dimethomorph, 4.6 and 8.1 days for mandipropamid, 4.7 and 8.2 days for myclobutanil, and 2.7 and 5 days for metalaxyl in squash fruit and leaf, respectively. Regarding the total surveyors, hazard quotient values for squash fruit and leaf were ≤1.03 × 10⁻³ and ≤2.39 × 10⁻³, respectively. These values in the case of true consumers were ≤3.14 × 10⁻³ and ≤3.91 × 10⁻¹, respectively. Full article

(This article belongs to the Special Issue Rapid Analytical, Removal and Transformation of Chemical Residues in Foods)

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12 pages, 1232 KiB

Open AccessArticle

Dissipation of Four Typical Insecticides on Strawberries and Effects of Different Household Washing Methods

by Wenting Wang, Jong-Wook Song, Seong-Hoon Jeong, Jung-Hoon Jung, Jong-Su Seo and Jong-Hwan Kim

Foods 2023, 12(6), 1248; https://0-doi-org.brum.beds.ac.uk/10.3390/foods12061248 - 15 Mar 2023

Cited by 1 | Viewed by 1646

Abstract

The dissipation patterns of chlorfenapyr, cyenopyrafen, indoxacarb, and spirotetramat on strawberries and the effects of different household washing methods were investigated. A risk assessment was also conducted by monitoring the insecticide residues detected. The concentrations ranged from 0.011 to 0.27 mg/kg for chlorfenapyr, [...] Read more.

The dissipation patterns of chlorfenapyr, cyenopyrafen, indoxacarb, and spirotetramat on strawberries and the effects of different household washing methods were investigated. A risk assessment was also conducted by monitoring the insecticide residues detected. The concentrations ranged from 0.011 to 0.27 mg/kg for chlorfenapyr, 0.064 to 0.99 mg/kg for cyenopyrafen, 0.042 to 0.53 mg/kg for indoxacarb, and from 0.25 to 1.3 mg/kg for spirotetramat, which were all below the maximum residue limits (MRLs) reported. Soaking the fruit in solution and then rinsing with running water (B) led to better residue removal (40.9 ± 23.7%) than only soaking in solution (A) (24.7 ± 22.5%). However, neither method decreased chlorfenapyr concentrations, suggesting that the physical–chemical properties of chlorfenapyr could also affect its removal on strawberries. Regarding the different washing solutions in method B, 3% vinegar (removal efficiency: 48.7%) and 3% salt (45.7%) were the most efficient, followed by 3% green tea (38.9%), and tap water only (24.6%). Additionally, the estimated risk quotients (RQs) for strawberry consumption for women were about 1.5 times higher than those observed for men, but both were lower than 1, suggesting minimal risk to humans. Full article

(This article belongs to the Special Issue Rapid Analytical, Removal and Transformation of Chemical Residues in Foods)

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16 pages, 1823 KiB

Open AccessArticle

Reduction in the Residues of Penthiopyrad in Processed Edible Vegetables by Various Soaking Treatments and Health Hazard Evaluation in China

by Jinming Chang, Li Dou, Yu Ye and Kankan Zhang

Foods 2023, 12(4), 892; https://0-doi-org.brum.beds.ac.uk/10.3390/foods12040892 - 19 Feb 2023

Viewed by 1126

Abstract

Tomato and cucumber are two vital edible vegetables that usually appear in people’s daily diet. Penthiopyrad is a new type of amide chiral fungicide, which is often used for disease control of vegetables (including tomato and cucumber) due to its wide bactericidal spectrum, [...] Read more.

Tomato and cucumber are two vital edible vegetables that usually appear in people’s daily diet. Penthiopyrad is a new type of amide chiral fungicide, which is often used for disease control of vegetables (including tomato and cucumber) due to its wide bactericidal spectrum, low toxicity, good penetration, and strong internal absorption. Extensive application of penthiopyrad may have caused potential pollution in the ecosystem. Different processing methods can remove pesticide residues from vegetables and protect human health. In this study, the penthiopyrad removal efficiency of soaking and peeling from tomatoes and cucumbers was evaluated under different conditions. Among different soaking methods, heated water soaking and water soaking with additives (NaCl, acetic acid, and surfactant) presented a more effective reduction ability than other treatments. Due to the specific physicochemical properties of tomatoes and cucumbers, the ultrasound enhances the removal rate of soaking for tomato samples and inhibits it for cucumber samples. Peeling can remove approximately 90% of penthiopyrad from contaminated tomato and cucumber samples. Enantioselectivity was found only during tomato sauce storage, which may be related to the complex microbial community. Health risk assessment data suggests that tomatoes and cucumbers are safer for consumers after soaking and peeling. The results may provide consumers with some useful information to choose better household processing methods to remove penthiopyrad residues from tomatoes, cucumbers, and other edible vegetables. Full article

(This article belongs to the Special Issue Rapid Analytical, Removal and Transformation of Chemical Residues in Foods)

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10 pages, 389 KiB

Open AccessArticle

Uptake of Soil-Residual Diazinon by Rotational Lettuce under Greenhouse Conditions

by Jihyun Yoon, Dajung Lim, Seungwon Lee, Jiyu Kim and Inseon Kim

Foods 2022, 11(21), 3510; https://0-doi-org.brum.beds.ac.uk/10.3390/foods11213510 - 04 Nov 2022

Cited by 1 | Viewed by 1429

Abstract

Pesticide residue is an increasing concern in rotational crop practices. The pesticide used for the primary crop may re-enter the secondary crop, thus exceeding pesticide levels set by the positive list system (PLS). As such, evaluation of pesticide residue translocated into rotational crops [...] Read more.

Pesticide residue is an increasing concern in rotational crop practices. The pesticide used for the primary crop may re-enter the secondary crop, thus exceeding pesticide levels set by the positive list system (PLS). As such, evaluation of pesticide residue translocated into rotational crops is required for ensuring pesticide safety. In this study, we investigated the residue pattern of diazinon translocated into lettuce as a typical rotational crop in Korea. Diazinon was used to treat greenhouse soil at the maximum annual application rate before crop planting. Diazinon residues in soil and lettuce were investigated using liquid chromatography/tandem mass spectroscopy and a modified quick, easy, cheap, effective, rugged, safe (QuEChERS) method. The limit of quantitation (LOQ) of diazinon was found as 0.005 mg/kg for the plant and soil samples. The recovery of diazinon at the LOQ and 10× the LOQ ranged from 100.2% to 108.7%. The matrix calibration curve showed linearity, with R² values > 0.998. Diazinon residue in soil dissipated over time after the initial treatment, generating first-order kinetics (R² = 0.9534) and having a half-life of about 22 days. The uptake ratio (UTR) of diazinon from the soil to the plant ranged from 0.002 to 0.026 over the harvest period. Considering the UTRs, diazinon residue in the edible leaf could exceed the PLS level (0.01 mg/kg) if lettuce is rotated in soil containing >0.357 mg/kg of diazinon. Based on our findings, to comply with the PLS, a 3-month plant-back interval is required following diazinon treatment and/or setting the maximum residue limit of diazinon for lettuce. Full article

(This article belongs to the Special Issue Rapid Analytical, Removal and Transformation of Chemical Residues in Foods)

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11 pages, 2991 KiB

Open AccessArticle

Development of Simultaneous Analytical Method for Imidazolinone Herbicides from Livestock Products by UHPLC-MSMS

by Hyo-Min Heo, Hyeong-Wook Jo, Hee-Ra Chang and Joon-Kwan Moon

Foods 2022, 11(12), 1781; https://0-doi-org.brum.beds.ac.uk/10.3390/foods11121781 - 16 Jun 2022

Cited by 2 | Viewed by 1733

Abstract

A simultaneous analytical method, which used LC/MSMS for imidazolinone herbicides from livestock products (egg, milk, beef, pork, and chicken) for monitoring, was developed with a QuEChERS preparation. A weighed sample (5 g) in a 50 mL conical tube was added to 0.1 M [...] Read more.

A simultaneous analytical method, which used LC/MSMS for imidazolinone herbicides from livestock products (egg, milk, beef, pork, and chicken) for monitoring, was developed with a QuEChERS preparation. A weighed sample (5 g) in a 50 mL conical tube was added to 0.1 M potassium phosphate dibasic solution (5 mL) and shaken for 10 min. After shaking, 0.5 mL of 6 N HCl and 5 mL of acetonitrile were added, and this solution was shaken for 10 min. Additionally, QuEChERS extraction salts (original method, 4 g MgSO₄, 1 g NaCl) were added to the sample in a 50 mL conical tube. The mixture was strongly shaken for 1 min and centrifuged at 3000× g for 10 min. The acetonitrile layer was purified with dSPE (150 mg MgSO₄, 25 mg C₁₈) and was centrifuged at 13,000× g for 5 min. The supernatant was filtered with a membrane filter (pore size: 0.2 μm) before analysis. The ME (%, matrix effect) range for almost all analytes was −6.56 to 7.11%. MLOD (method limit of detection) and MLOQ (method limit of quantitative) values were calculated by the S/N ratio. MLOQs were 0.01 mg/kg. The linear correlation coefficients (R²) were >0.99 with the range of 0.5~25 μg/kg for all of the imidazolinone herbicides. The recoveries (of imidazolinone herbicides) were in the range of 76.1~110.6% (0.01 mg/kg level), 89.2~97.1% (0.1 mg/kg level), and 94.4~104.4% (0.5 mg/kg level). These are within the validation criteria (to recover 70–120% with RSD <20%). The method demonstrated the simple, rapid, high throughput screening and quantitative analysis of imidazolinone herbicide residues for monitoring in livestock products. Full article

(This article belongs to the Special Issue Rapid Analytical, Removal and Transformation of Chemical Residues in Foods)

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15 pages, 2052 KiB

Open AccessArticle

Research on Rapid Detection Technology for β₂-Agonists: Multi-Residue Fluorescence Immunochromatography Based on Dimeric Artificial Antigen

by Miaomiao Liu, Biao Ma, Yaping Wang, Erjing Chen, Jiali Li and Mingzhou Zhang

Foods 2022, 11(6), 863; https://0-doi-org.brum.beds.ac.uk/10.3390/foods11060863 - 18 Mar 2022

Cited by 11 | Viewed by 1653

Abstract

To detect two types of β₂-agonist residues at the same time, we coupled two haptens of clenbuterol (CLE) and ractopamine (RAC) to the same carrier protein through diazotization to prepare dimeric artificial antigen, and a fluorescent lateral flow immunoassay method based [...] Read more.

To detect two types of β₂-agonist residues at the same time, we coupled two haptens of clenbuterol (CLE) and ractopamine (RAC) to the same carrier protein through diazotization to prepare dimeric artificial antigen, and a fluorescent lateral flow immunoassay method based on europium nanoparticles (EuNP-FLFIA) was established by combining polyclonal antibodies with europium nanoparticles to form probes. Under optimized conditions, the EuNP-FLFIA could simultaneously detect eight aniline-type and one phenol-type β₂-agonists, and the limits of detection (LOD) were 0.11–0.19 ng/mL and 0.12 ng/mL, respectively. The recovery rate of this method was 84.00–114.00%. This method was verified by liquid chromatography–tandem mass spectrometry (LC-MS/MS), and the test results were consistent (R² > 0.98). Therefore, the method established in this study could be used as a high-throughput screening for the efficient and sensitive detection of β₂-agonists in food. Full article

(This article belongs to the Special Issue Rapid Analytical, Removal and Transformation of Chemical Residues in Foods)

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