PESTICIDES IN THE MODERN WORLD – TRENDS IN PESTICIDES ANALYSIS Edited by Margarita Stoytcheva Pesticides in the Modern World – Trends in Pesticides Analysis Edited by Margarita Stoytcheva Published by InTech Janeza Trdine 9, 51000 Rijeka, Croatia Copyright © 2011 InTech All chapters are Open Access articles distributed under the Creative Commons Non Commercial Share Alike Attribution 3.0 license, which permits to copy, distribute, transmit, and adapt the work in any medium, so long as the original work is properly cited. After this work has been published by InTech, authors have the right to republish it, in whole or part, in any publication of which they are the author, and to make other personal use of the work. Any republication, referencing or personal use of the work must explicitly identify the original source. Statements and opinions expressed in the chapters are these of the individual contributors and not necessarily those of the editors or publisher. No responsibility is accepted for the accuracy of information contained in the published articles. The publisher assumes no responsibility for any damage or injury to persons or property arising out of the use of any materials, instructions, methods or ideas contained in the book. Publishing Process Manager Sandra Bakic Technical Editor Teodora Smiljanic Cover Designer Jan Hyrat Image Copyright flashgun, 2010. Used under license from Shutterstock.com First published September, 2011 Printed in Croatia A free online edition of this book is available at www.intechopen.com Additional hard copies can be obtained from orders@intechweb.org Pesticides in the Modern World – Trends in Pesticides Analysis, Edited by Margarita Stoytcheva p. cm. ISBN 978-953-307-437-5 free online editions of InTech Books and Journals can be found at www.intechopen.com Contents Preface IX Part 1 Pesticides: Overview 1 Chapter 1 Identity, Physical and Chemical Properties of Pesticides 3 Zacharia, James Tano Chapter 2 Thermodynamic Properties and Crystallization Behavior of Pesticide Imidacloprid 21 Zhou Cairong Chapter 3 Photolysis of Some Benzimidazole Based Pesticides 43 Yaser A. Yousef and Talal. S. Akasheh Chapter 4 Pesticides Empty Containers (EPC) in the Area of Ouagadougou: Actors, Risks and Prospects of Secure Management 54 Gomgnimbou P.K Alain and Ouédraogo W. Osée Chapter 5 Electrochemical Detoxification of Obsolete Pesticides Stocks 71 R. Salghi, M. Errami, B. Hammouti and L. Bazzi Chapter 6 Advances in Analytical Methods for Organophosphorus Pesticide Detection 93 Tova A. Samuels and Sherine O. Obare Chapter 7 Organophosphorus Pesticides Analysis 143 Margarita Stoytcheva and Roumen Zlatev Chapter 8 New Methodologies for Assessing the Presence and Ecological Effects of Pesticides in Doñana National Park (SW Spain) 165 Carmen Pueyo, José-Luis Gómez-Ariza, Miguel-Angel Bello-López, Rut Fernández-Torres, Nieves Abril, José Alhama, Tamara García-Barrera and Juan López-Barea VI Contents Part 2 Chromatographic Pesticides Analysis 197 Chapter 9 Modern Sample Preparation Techniques for Pesticide Analysis 199 Lesego C. Mmualefe, Christopher Mpofu and Nelson Torto Chapter 10 Modern Extraction Techniques for Pesticide Residues Determination in Plant and Soil Samples 221 Rada Ðurović and Tijana Ðorđević Chapter 11 Cloud Point Extraction of Pesticide Residues 247 Hayati Filik and Sema Demirci Çekiç Chapter 12 Determination of Pesticides in Complex Samples by One Dimensional (1D-), Two-Dimensional (2D-) and Multidimensional Chromatography 281 Tomasz Tuzimski Chapter 13 Recent Techniques Applied for Pesticides Identification and Determination in Natural Products and Its Impact to Human Health Risk 319 Abd El-Moneim M.R. Afify Chapter 14 Pesticide Residues in Natural Products with Pharmaceutical Use: Occurrence, Analytical Advances and Perspectives 357 Andrés Pérez-Parada, Marcos Colazzo, Natalia Besil, Eduardo Dellacassa, Verónica Cesio, Horacio Heinzen and Amadeo R. Fernández-Alba Chapter 15 Non-Targeted Analyses for Pesticides Using Deconvolution, Accurate Masses, and Databases – Screening and Confirmation 391 Chin-Kai Meng, Mike Szelewski, Jerry Zweigenbaum, Peter Fürst and Eva Blanke Chapter 16 Applications of Hadamard Transform-Gas Chromatography/Mass Spectrometry (HT-GC/MS) to the Detection of Pesticides in Rice 413 Cheng-Huang Lin and Chien-Hung Lin Chapter 17 Highlights of Mass Spectrometric Methodologies in Environmental Pollution 425 Mohamed Attya, Brunella Cavaliere, Fabio Mazzotti, Antonio Tagarelli and Giovanni Sindona Part 3 Emerging Methods of Pesticides Analysis 451 Chapter 18 Chemically Modified Electrodes for Detection of Pesticides 453 Ayanthi Navaratne and Namal Priyantha Contents VII Chapter 19 Voltammetric Analysis of Pesticides 465 Ignas Tonle K. and Emmanuel Ngameni Chapter 20 The Potential of Flow-Based Optosensing Devices for Pesticide Assessment 489 Maria Luisa Fernández-de Córdova and Pilar Ortega-Barrales Preface Volume 1 of the unique book series “Pesticides in the Modern World” is a collection of 20 chapters addressing issues associated with pesticides detection, identification, characterisation, and determination, organized in three sections. Chapters 1-3 included in the first book section provide on overview on the recognized principles for pesticides classification, and supply detailed data on pesticides physical properties (vapour pressure, solubility, soil adsorption coefficient, specific characteristics), and chemical interactions including oxidation, reduction, hydrolysis, and photolysis. The thermodynamic properties of imidacloprid in particular are investigated in order to solve the problem of its separation and purification. Environmental risks and safe pesticides management topics are discussed in Chapter 4. The electrochemical oxidation as a method of detoxification of obsolete pesticides stocks is suggested in Chapter 5. Chapters 6 and 7 offer an exhaustive revision of the advanced chromatographic and alternative sensors and biosensors-based methods for organophosphorus pesticides determination. Chapter 8 comments on the improvement of the sensitivity and selectivity of some chromatographic techniques for pesticides analysis, and on the utility of the environmental proteomic approach in environmental pollutants assessment. The second book section is devoted to the chromatographic pesticides quantification. Chapters 9-11 discuss various strategies for sample preparation, with emphasis on the processes of extraction. The basic principles of the modern extraction techniques, such as: accelerated solvent extraction, supercritical fluid extraction, microwave assisted extraction, solid phase extraction, solid phase microextraction, matrix solid phase dispersion extraction, cloud point extraction, and QuEChERS are comprehensively described and critically evaluated. The recent advances in the multidimensional chromatographic separation techniques are highlighted in Chapter 12. Chapters 13 and 14 cover topics on pesticides residues analysis in natural products, including sample preparation procedures. In Chapter 15 it is presented the deconvolution approach in the non-targeted pesticide analysis, allowing trace level pesticides determination. The application of the Hadamard transformation to gas chromatography/mass spectrometry for the sensitive detection of pesticides in rice is X Preface commented in Chapter 16. The efficiency of gas chromatography/mass spectrometry is discussed in Chapter 17. The third book section (Chapters 18-20) describes some alternative analytical approaches to the conventional methods of pesticides determination. These include voltammetric techniques making use of electrochemical sensors and biosensors, and solid-phase spectrometry combined with flow-injection analysis applying flow-based optosensors. Their remarkable analytical features are associated with the simple operation procedure without or with a minimum sample pretreatment, and the high sensitivity of the determinations. Overall, the book offers a professional look on the recent achievements and emerging trends in pesticides analysis. It could act as an excellent reference for the specialists, involved in pesticides detection, identification, and determination. All the contributing authors are gratefully acknowledged for their time and efforts in preparing the different chapters, and for their interest in the present project. Margarita Stoytcheva, Ph.D. Institute of Engineering Mexicali, Baja California Mexico [...]... representative pesticides 16 Pesticides in the Modern World – Trends in Pesticides Analysis 4 Chemical properties of pesticides Following the release of pesticides in the environment, they undergo a complex series of interdependent processes that are collectively called chemodynamics of pesticides The chemodynamic processes that a pesticide undergoes is essentially determined by its inherent physico-chemical... and the corresponding crop yield in some countries/areas 6 Pesticides in the Modern World – Trends in Pesticides Analysis 2 Identity of pesticides 2.1 How can pesticides be identified? Many of the pesticides that we use in our crops, gardens or domestic animals, are often a mixture of several chemicals mixed together in desired proportions suspended in appropriate carrier or diluent materials These... classification that gives the clue of the effficacy, physical and chemical properties of the respective pesticides, the knowledge of which is very important in the mode of application, precautions that need to be taken 8 Pesticides in the Modern World – Trends in Pesticides Analysis during application and the application rates Based on chemical classification, pesticides are classified into four main groups namely;... one third of the potential world crop harvest was lost to pests A further illustration to the pest problem in the world is shown in table 1.1 (Hellar, 2002) Insect pests and rodents also account for a big loss in stored agricultural products Internally feeding insects feed on grain endosperm and the germ the result of which is the loss in grain weight, reduction in nutritive value of the grain and deterioration... with the ensuing release of electron thus changing the molecule Photolysis reactions are important for degrading organic molecules in the upper atmosphere, in shallow aquatic environment, on foliage and on the surface of soils Pyrethroids are particularly susceptible to photolysis reactions The total decomposition of a pesticide in the 18 Pesticides in the Modern World – Trends in Pesticides Analysis. .. 2006; DING et al., 2000) As long as crystallization behavior is observed and 22 Pesticides in the Modern World – Trends in Pesticides Analysis the data for the pure substances are known it is possible to use the data obtained in any solid-liquid equilibrium experiment to calculate the activity coefficient in the liquid phase The study of solid-liquid equilibrium of binary/ternary mixtures provides information... cinerariaefolium) The insecticidal components of pyrethrum flowers are the optically active esters derived from (+)-trans-chrysanthemic acid and (+)-trans-pyrethroic acid 10 Pesticides in the Modern World – Trends in Pesticides Analysis Pyrethroids are acknowledged of their fast nocking down effect against insect pests, low mammalian toxicity and facile biodegradation Although the naturally occurring... delouse soldiers in the World War II and in the public health for the control of mosquitoes which are the vectors for malaria Following the success of DDT, such other chemicals were synthesized to make this era what Rachel Carson (1962) in her book "The Silent Spring" described as the era of "rain of chemicals” The intensive use of pesticides in agriculture is also well known to be coupled with the "green... Wiley and Sons Inc New York, USA 20 Pesticides in the Modern World – Trends in Pesticides Analysis Keneth, M (1992) The DDT Story, The British Crop Protection Council, London, UK Carson, R L (1962) Silent Spring, The Riverside Press Cambridge, USA Vocke, G (1986) The Green Revolution for Wheat in Developing Countries, US Department of Agriculture, USA Hellar, H (2002) Pesticides Residues in Sugarcane... revolution was a worldwide agricultural movement that began in Mexico in 1944 with a primary goal of boosting grain yields in the world that was already in trouble with food supply to meet the demand of the then rapidly growing human population The green revolution involved three major aspects of agricultural practices, among which the use of pesticides was an integral part Following its success in Mexico, . PESTICIDES IN THE MODERN WORLD – TRENDS IN PESTICIDES ANALYSIS Edited by Margarita Stoytcheva Pesticides in the Modern World – Trends in Pesticides Analysis. Pesticides in the Modern World – Trends in Pesticides Analysis 8 during application and the application rates. Based on chemical classification, pesticides are classified into four main. 2.6 Latin America 0.2 2.0 Oceania 0.2 1.6 Africa 0.1 1.2 Table 1.2 Pesticides use and the corresponding crop yield in some countries/areas Pesticides in the Modern World – Trends in Pesticides