Application Progress of Chromatographic Analytical Methods in Agriculture

A special issue of Agriculture (ISSN 2077-0472). This special issue belongs to the section "Agricultural Product Quality and Safety".

Deadline for manuscript submissions: 20 June 2024 | Viewed by 6438

Special Issue Editors


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Guest Editor
Laboratory of Chemical Control of Pesticides, Department of Pesticides Control and Phytopharmacy Benaki Phytopathological Institute, GR-14561 Kiffisia, Athens, Greece
Interests: pesticide residues in plant/animal products and environmental samples; analytical methods; environmental monitoring; pesticides; contaminants; method validation; chromatography; mass spectrometry; risk assessment

E-Mail Website
Guest Editor
Laboratory of Chemical Control of Pesticides, Department of Pesticides Control and Phytopharmacy Benaki Phytopathological Institute, GR-14561 Kiffisia, Athens, Greece
Interests: gas and liquid chromatography; tandem mass spectrometry; plant protection products; pesticide residues; plant metabolites; volatile compounds

Special Issue Information

Dear Colleagues,

Analytical Chemistry and particularly chromatographic analytical methods play a key role for the attainment of the UN Sustainable Development Goals that are directly or indirectly connected to Agriculture since the solution to any problem demands knowledge of the existing situation.

Chromatographic applications involve either target analysis, i.e., the development and validation of methods for the determination of known compounds, or non-targeted analysis, i.e., methods aiming at characterizing the chemical composition of complex samples, identifying unknown compounds, and/or classifying samples, without prior knowledge regarding the chemical content of the samples. Pesticide residues, heavy metals, xenobiotic compounds and other chemical substances are monitored and regulated by legislation in samples of plant origin, water, soil, air, and other agricultural by-products, as to safeguard an acceptable potential risk for human health, food safety and the environment.

Contamination of the agro-environment with pollutants applied or produced through agricultural practices, smart agriculture for food quality, determination of plant metabolites aiming to detect and/or measure plant responses under particular conditions, or confirmation of alternative approaches of agricultural practices are examples of the sectors of Agriculture in which analytical methods can applied. 

This Special Issue aims to cover the wide scope of chromatographic analytical methods applied in all sectors of agriculture and include interdisciplinary studies embracing agriculture with disciplines of chemistry, biology, and engineering. Research articles are expected to cover various sample preparation procedures, chromatographic and detection techniques. Detected compounds (including metabolites, degradation products, co-formulants, impurities and volatile compounds, etc) and tested substrates can be of great variance.

All types of articles, such as original research, opinions, and reviews are welcome.

Dr. Eleftheria Bempelou
Dr. George Balayiannis
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Agriculture is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • analytical methods
  • chromatography
  • pesticides
  • pollutants
  • agro-environment
  • metabolites
  • target/non-target analysis

Published Papers (5 papers)

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Research

18 pages, 3731 KiB  
Article
Comparative Analysis of Anisotropic Lipophilicity of a Series of 6-Chloro-1,3,5-Triazines Determined in Reversed Phase Ultra High Performance Liquid Chromatography System
by Strahinja Kovačević, Milica Karadžić Banjac, Jasmina Anojčić, Vojislav Banjac, Petar Ilić, Benjamin Salaković, Sanja Podunavac-Kuzmanović and Lidija Jevrić
Agriculture 2023, 13(12), 2212; https://doi.org/10.3390/agriculture13122212 - 28 Nov 2023
Viewed by 785
Abstract
Triazine derivatives are well-known commercially available compounds used for selective weed control in different crops, such as corn and sugarcane. Some of them are considered persistent organic compounds in the environment and it is important to improve the features of herbicide formulae, to [...] Read more.
Triazine derivatives are well-known commercially available compounds used for selective weed control in different crops, such as corn and sugarcane. Some of them are considered persistent organic compounds in the environment and it is important to improve the features of herbicide formulae, to estimate their physicochemical properties and to determine their retention behavior in modern analytical techniques that can be used in the determination of pesticides in environmental samples. The present study deals with a comprehensive analysis of the chromatographic behavior of a series of 6-chloro-1,3,5-triazines with alkyl and cycloalkyl substituents, among which some compounds possess herbicidal and fungicidal activity. The anisotropic lipophilicity of triazine derivatives was determined using reversed-phase ultra high performance liquid chromatography with octadecyl and phenyl columns and applying binary (methanol/water and acetonitrile/water) and ternary (methanol/acetonitrile/water) mobile phases under isocratic conditions. The retention data were analyzed using chemometric pattern recognition methods (hierarchical cluster analysis and principal component analysis) and sum of ranking differences method. The obtained results are excellent indicators of the retention behavior and the lipophilicity of the analyzed series of triazines and can serve as an outstanding basis for the development of new chromatographic methods for the determination of triazines in environmental samples. Full article
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16 pages, 8275 KiB  
Article
Electrophysiological Responses of Curculio elephas (Coleoptera: Curculionidae) to Chestnut Plant Volatiles
by Eirini Anastasaki, Aikaterini Psoma, Savvina Toufexi, Georgios Partsinevelos, Dimitrios Papachristos, Dimitrios Avtzis and Panagiotis Milonas
Agriculture 2023, 13(10), 1991; https://doi.org/10.3390/agriculture13101991 - 13 Oct 2023
Viewed by 1063
Abstract
Curculio elephas is an oligophagous insect, attacking fruits of chestnut (Castanea spp.) and oak (Quercus spp.). It is considered one of the most important pests of European chestnut (Castanea sativa) in Europe and it occurs in a continuous range [...] Read more.
Curculio elephas is an oligophagous insect, attacking fruits of chestnut (Castanea spp.) and oak (Quercus spp.). It is considered one of the most important pests of European chestnut (Castanea sativa) in Europe and it occurs in a continuous range throughout Greece. The aim of this study was to identify the potential volatile organic compounds (VOCs) from chestnut reproductive plant tissues (catkin, nut, and bur) acting as attractants for C. elephas adults to be used for the development of a monitoring system integrating pest management tools. VOCs were sampled in situ during spring and autumn of 2021 and 2022 in different areas of Greece. For the collection and identification of VOCs, the dynamic-headspace technique combined with gas chromatography–mass spectrometry (GC–MS), was employed. In total, 122 compounds from these tissues were detected, with most of them being terpenes (>80%). Further analysis showed that chestnut trees release different VOCs depending on their developmental stage. Antennae of both male and female chestnut weevil adults responded to terpenes, green leaf volatiles, and methyl salicylate. Identification of semiochemicals for manipulating weevils’ behavior will contribute to the development of efficient monitoring tools for the detection and management of this pest. Full article
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16 pages, 1750 KiB  
Article
Adjuvant Effects on Pyraclostrobin and Boscalid Residues, Systemic Movement, and Dietary Risk in Garlic under Field Conditions
by Paraskevas Parlakidis, George Adamidis, Christos Alexoudis, Paschalina Pythoglou, Sotirios Papadopoulos and Zisis Vryzas
Agriculture 2023, 13(8), 1636; https://doi.org/10.3390/agriculture13081636 - 19 Aug 2023
Cited by 1 | Viewed by 1146
Abstract
Adjuvants are supplemental substances added to pesticide tank mixtures to enhance their efficacy by altering the dispersing, emulsifying, spreading, sticking, and wetting properties of the spray mixture. The goals of this study were an assessment of the effectiveness of pyraclostrobin and boscalid against [...] Read more.
Adjuvants are supplemental substances added to pesticide tank mixtures to enhance their efficacy by altering the dispersing, emulsifying, spreading, sticking, and wetting properties of the spray mixture. The goals of this study were an assessment of the effectiveness of pyraclostrobin and boscalid against garlic rust; the fungicide’s dissipation and translocation within plant tissue in the presence of commercial adjuvants Dash® HC EC; and the validation of an analytical method for concurrently determining boscalid and pyraclostrobin in green garlic and garlic bulbs. Pyraclostrobin and boscalid retention in green garlic and the dietary exposure risks were also evaluated. The adjuvant Dash® HC EC is an emulsifiable concentrate containing fatty acids, methyl esters, and alkoxylated alcohol–phosphate esters. The test plots were sprayed with the maximum recommended dosage of 400.5 g a.i. ha−1 boscalid and 100.5 g a.i. ha−1 pyraclostrobin. The residues of pyraclostrobin and boscalid in garlic bulb and green garlic samples were determined using a mini-Luke multi-residue solvent extraction method paired with a high-performance liquid chromatography diode array detector (HPLC–DAD). This method is based on the extraction of a homogeneous sample with acetone, petroleum ether, and dichloromethane. Boscalid and pyraclostrobin recoveries in green garlic and garlic bulbs ranged from 71% to 107% on average, with a relative standard deviation (RSD) of 6.8% to 18.1%, and limits of quantification were 0.02 mg/kg. In green garlic and garlic bulbs, boscalid residues ranged from 0.14 to 3.51 mg/kg and pyraclostrobin from lower than LOQ to 1.43 mg/kg, during the experiment. The adjuvant increased the fungicidal efficacy of the fungicides and their retention on green garlic. Although boscalid is considered a nonsystemic fungicide, it showed higher translocation from garlic leaves to garlic bulbs than pyraclostrobin. Regarding the dietary risk assessment, the use of the adjuvant in a tank mixture with boscalid and pyraclostrobin is considered safe 14 days after application, which agrees with the recommended PHI. Full article
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10 pages, 1280 KiB  
Article
N-Nitrosamine Impurities in Ethalfluralin: Determination of an Overlooked Deleterious Source in Pesticides
by George P. Balayiannis and Helen Karasali
Agriculture 2023, 13(5), 1104; https://doi.org/10.3390/agriculture13051104 - 22 May 2023
Viewed by 1398
Abstract
N-nitrosamines are a class of carcinogenic chemical compound. Considering the large-scale application of agrochemicals globally, the elimination of N-nitrosamines from pesticides should be a priority for manufacturers and regulators. A set of methods was developed and validated for the determination of [...] Read more.
N-nitrosamines are a class of carcinogenic chemical compound. Considering the large-scale application of agrochemicals globally, the elimination of N-nitrosamines from pesticides should be a priority for manufacturers and regulators. A set of methods was developed and validated for the determination of the toxicologically relevant N-nitrosamine impurity of ethalfluralin (ethyl-N-(2-methylallyl) N-nitroso amine—EMANA) in 33% w v−1 emulsifiable concentrate (EC) formulations. Solid Phase Extraction (SPE) was compared with the “dilute and shoot” approach. Gas chromatography (GC) was combined with Flame Ionization Detection (FID) and mass spectrometry (MS). For MS, two mass filtering modes (Selective Ion Monitoring—SIM, tandem mass spectrometry—MS/MS) and two ionization modes (Electron Ionization—EI, Positive chemical ionization—PCI) were applied. It was concluded that, in the case of samples with high nitrosamine concentration (>90 μg g−1), the “dilute and shoot” approach can be applied without compromising the quality of the results. SPE, however, is required to attain the LOQ (0.33 μg g−1) with good recovery (97.4–110.67%), linearity (R > 0.99) and precision (%RSD 0.68–1.74). The LOQ supersedes the limit set by EFSA (1 μg g−1) in the Technical Active Substance—TAS. The concentration range of the methods is 0.05–110 μg g−1. The methods were applied for the official surveillance program of the Greek agrochemicals market. Full article
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17 pages, 2377 KiB  
Article
Toxicity of Insecticides in the Adult and Larva Olive Fruit Fly, after Estimation of the Dislodgeable Foliar and Fruit Residues in Olive Trees by LC-MS/MS and GC-MS/MS
by Eleftheria Bempelou, Kyriaki Varikou, Chris Anagnostopoulos, Angeliki Charalampous, Nikolia Samari, Leonidas Economou, Nikolaos Garantonakis and Konstantinos Liapis
Agriculture 2023, 13(3), 543; https://doi.org/10.3390/agriculture13030543 - 23 Feb 2023
Cited by 2 | Viewed by 1393
Abstract
“Can systemic insecticides be used in bait spots in order to kill the adult olive fly?” Effort was directed toward providing an answer to that question. Both field and laboratory tests were implemented to detect the dislodgeable residues of dimethoate, phosmet and b-cyfluthrin [...] Read more.
“Can systemic insecticides be used in bait spots in order to kill the adult olive fly?” Effort was directed toward providing an answer to that question. Both field and laboratory tests were implemented to detect the dislodgeable residues of dimethoate, phosmet and b-cyfluthrin in olive leaves and fruit using the LC-MS/MS and GC-MS/MS chromatographic techniques. Residues of dimethoate declined more over time than those of phosmet, while levels of beta-cyfluthrin remained almost stable, both in leaves and fruit. Additionally, significantly higher and faster toxicity of dimethoate and beta-cyfluthrin (>92%) compared to phosmet (80%) to fly adults was shown, which was reduced significantly after a two-week period. Conversely, 100% mortality of the larval stages within olive flesh was observed at the 2nd day for dimethoate and at the 7th day for phosmet. Although phosmet was not expected to contribute to preventing larval development, its application in bait sprays presented similar toxicity to that of dimethoate. However, no larval toxicity was recorded in beta-cyfluthrin. As a primary conclusion, we recommend the avoidance of the use of systemic insecticides in bait sprays. Full article
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