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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
Analytical Methods for Environmental Contaminants of Emerging Concern Provides the analytical methodology required to detect different families of organic compounds of emerging concern (CECs) from environmental samples Most contaminants of emerging concern (CECs) --such as pharmaceuticals, personal care products, pesticides, sunscreens, perfluorinated compounds, and microplastics--have been present in the environment for years, yet some have only recently been identified, and many of these organic compounds remain unregulated. Analytical methods have been developed to determine the toxicity and risk of different families of CECs. Analytical Methods for Environmental Contaminants of Emerging Concern presents the methods currently available to determine families of organic CECs in environmental samples. Each section of the book is devoted to a particular family of CECs, covering different analytical methods supported by examples of both cutting-edge research and commonly used methods. An international panel of experts describes every step of the analytical procedures, including sample preparation, chromatographic separation coupled to mass spectrometry or other instrumental techniques. Specific requirements are linked to the properties of the contaminants and the sample matrix for each procedure presented. Throughout the book, in-depth case studies of analytical procedures for CEC extraction, separation, and determination are presented to help readers transfer the analytical methods to their laboratories. * Provides detailed descriptions of various approaches for determining each group of CECs in environmental samples * Covers different types of aqueous, solid, and atmospheric samples * Includes up-to-date information on CEC properties, relevant legislation, reported or potential metabolites/transformation products, and environmental occurrence * Addresses CECs such as novel psychoactive substances, artificial sweeteners, musk fragrances, disinfection byproducts, and microplastics * Offers practical tips and advice on special care procedures to assist readers in CEC determination Analytical Methods for Environmental Contaminants of Emerging Concern is an essential reference and guide for advanced students and researchers in analytical chemistry and science, environmental science, forensic science, and specialized subjects related to analytical chemistry.
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Analytical Methods for Environmental Contaminants of Emerging Concern
Edited byNúria Fontanals and Rosa Maria MarcéUniversitat Rovira i Virgili, Spain
This edition first published 2022© 2022 John Wiley & Sons Ltd
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Contents
Cover
Title page
Copyright
Contributors
Preface
1 Pesticides
1.1 Overview of Pesticides
1.1.1 Properties
1.1.2 Legislation
1.1.3 Reported or Potential Metabolites and/or Transformation Products
1.1.4 Occurrence in the Environment
1.2 Sample Preparation and Collection
1.2.1 Protocols for Collecting and Preparing Samples
1.2.2 Sample Extraction and Clean-up
1.3 Determination of Pesticides
1.3.1 Development of the Instrumental Method
1.3.1.1 Chromatography
1.3.1.2 Detection
1.3.2 Figures of Merit
1.3.3 Hints and Tips
1.4 Future Directions and Challenges
Acknowledgments
Bibliography
2 Pharmaceuticals
2.1 Overview of Pharmaceuticals
2.1.1 Properties
2.1.2 Reported or Potential Metabolites and/or Transformation Products
2.1.3 Occurrence
2.1.4 Legislation
2.2 Sampling and Sample Preparation
2.2.1 Solid Samples
2.2.2 Water Samples
2.3 Analytical Techniques for the Determination of Pharmaceuticals
2.3.1 Gas Chromatography and Gas Chromatography Coupled to Mass Spectrometry
2.3.2 Liquid Chromatography and Liquid Chromatography Coupled to Mass Spectrometry
2.4 Conclusion and Future Trends
References
3 Personal Care Products
3.1 Overview of Personal Care Products
3.1.1 Properties
3.1.2 Legislation
3.1.3 Transformation Products
3.1.4 Occurrence in the Environment
3.2 Sample Preparation for PCPs in the Aquatic Environment
3.2.1 Sorbent-based Methodologies
3.2.1.1 Solid-phase Extraction
3.2.1.2 Fabric Phase Sorptive Extraction
3.2.1.3 Stir-bar Sorptive Extraction
3.2.1.4 Solid-phase Microextraction
3.2.2 Liquid-based Extraction Techniques
3.2.2.1 Microextraction Liquid Phase Approaches: DLLME, SDME, USAEME
3.3 Determination of Personal Care Products
3.4 Future Directions and Challenges
Acknowledgements
References
4 New Psychoactive Substances
4.1 Overview of New Psychoactive Substances
4.1.1 Properties
4.1.2 NPS Market, Dynamics and International Control
4.1.3 Potential Metabolites and/or Transformation Products
4.1.4 Occurrence in the Environment
4.2 Sample Preparation and Collection
4.2.1 Urban Wastewater
4.2.1.1 Protocols for Collecting and Preparing Samples
4.2.1.2 Extraction Procedures and Clean-up
4.2.2 Other Environmental Matrices
4.3 Determination of New Psychoactive Substances
4.3.1 Development of the Instrumental Method
4.3.1.1 Chromatographic Separation
4.3.1.2 Detection
4.3.2 Figures of Merit
4.3.3 Hits and Tips
4.4 Future Direction and Challenges
Acknowledgments
References
5 Artificial Sweeteners
5.1 Overview of Artificial Sweeteners
5.1.1 Properties
5.1.2 Legislation and Environmental Risk Assessment
5.1.3 Reported or Potential Metabolites and/or Transformation Products
5.1.4 Occurrence in the Environment
5.2 Sample Preparation and Collection
5.2.1 Protocols for Collecting and Preparing Samples
5.2.2 Sample Extraction and Clean-up
5.3 Determination of Artificial Sweeteners
5.3.1 Development of the Instrumental Method
5.3.1.1 Chromatography
5.3.1.2 Detection
5.3.2 Figures of Merit
5.3.3 Hints and Tips
5.4 Future Directions and Challenges
References
6 Perfluorinated Substances
6.1 Overview of Perfluoroalkyl Substances
6.1.1 Properties
6.1.2 Legislation
6.1.3 Reported or Potential Metabolites and/or Transformation Products
6.1.4 Occurrence in the Environment
6.2 Sample Preparation and Collection
6.2.1 Protocols for Collecting and Preparing Samples
6.2.2 Sample Extraction and Clean-up
6.3 Determination of PFASs
6.3.1 Development of the Instrumental Method
6.3.1.1 Chromatography-Mass Spectrometry
6.3.1.2 Biosensors
6.3.2 Figures of Merit
6.3.3 Hints and Tips
6.4 Future Directions and Challenges
References
7 High Production Volume Chemicals
7.1 Overview of High Production Volume Chemicals
7.1.1 Properties
7.1.2 Legislation
7.1.3 Reported or Potential Metabolites and/or Transformation Products
7.1.4 Occurrence
7.2 Sample Preparation and Collection
7.2.1 Protocols for Collecting and Preparing Samples
7.2.1.1 Water
7.2.1.2 Air and Dust
7.2.1.3 Soil, Sediments, and Sludge
7.2.1.4 Biota
7.2.2 Sample Extraction and Clean-Up
7.2.2.1 Water
7.2.2.2 Air and Dust
7.2.2.3 Soil, Sediments, and Sludge
7.2.2.4 Biota
7.3 Determination of High Production Volume Chemicals
7.3.1 Development of the Instrumental Method
7.3.2 Figures of Merit
7.3.3 Hints and Tips
7.4 Future Directions and Challenges
Acknowledgments
References
8 Musk Fragrances
8.1 Overview of Musk Fragrances
8.1.1 Properties
8.1.2 Legislation
8.1.3 Reported or Potential Metabolites and/or Transformation Products
8.1.4 Occurrence in the Environment
8.1.4.1 Occurrence in Wastewater and Sewage Sludge
8.1.4.2 Occurrence in Surface Water, Soils, Sediments and Air
8.1.4.3 Occurrence in Biota
8.2 Sample Preparation and Collection
8.2.1 Protocols for Collecting and Preparing Samples
8.2.1.1 Air Samples
8.2.1.2 Water Samples
8.2.1.3 Sludge, Soil and Sediment Samples
8.2.1.4 Biota
8.2.2 Sample Extraction and Clean-up
8.2.2.1 Air Samples
8.2.2.2 Water Samples
8.2.2.3 Sludge, Soil and Sediment Samples
8.2.2.4 Biota
8.3 Determination of Musk Fragrances
8.3.1 Chromatography
8.3.2 Detection
8.4 Future Directions and Challenges
References
9 Disinfection Byproducts in Water
9.1 Overview of Main DBP Classes
9.1.1 Properties
9.1.2 Legislation
9.1.3 Potential Metabolites and/or Transformation Products
9.1.4 Occurrence in the Environment
9.2 Sample Preparation and Collection
9.2.1 Protocols for Collecting and Preparing Samples
9.2.2 Sample Extraction and Clean-up
9.3 Determination of DBPs
9.3.1 Development of the Instrumental Method
9.3.1.1 Chromatography
9.3.1.2 Detection
9.3.2 Figures of Merit
9.3.2.1 Linearity
9.3.2.2 Precision and Accuracy
9.3.2.3 Sensitivity
9.3.3 Hints and Tips
9.4 Future Directions and Challenges
Acknowledgements
References
10 Microplastics
10.1 Overview of Micro- and Nanoplastics
10.1.1 Properties
10.1.2 Legislation
10.1.3 Origin and Distribution
10.1.4 Occurrence in the Environment
10.1.4.1 Water Systems
10.1.4.2 Sediments
10.1.4.3 Biota
10.2 Sample Preparation and Collection
10.2.1 Protocols for Collecting and Preparing Samples
10.2.1.1 Water
10.2.1.2 Sediment
10.2.1.3 Biota
10.2.2 Sample Extraction and Clean-up
10.2.2.1 Separation
10.2.2.2 Matrix Removal by Digestion
10.3 Determination of MNPLs
10.3.1 Physical Characterization
10.3.2 Chemical Characterization
10.4 Future Directions and Challenges
Acknowledgments
References
Index
End User License Agreement
List of Illustrations
Chapter 1
Figure 1.1
Forty-five TPs originating from...
Figure 1.2
Metabolite behavior according to the...
Figure 1.3
Neonicotinoid insecticides in the environment...
Figure 1.4
Pesticide families detected in (A...
Figure 1.5
Chromatograms of the targeted pesticides...
Chapter 2
Figure 2.1
Selected properties of pharmaceuticals.
Chapter 3
Figure 3.1
Pathways of personal care products...
Chapter 4
Figure 4.1
Number of NPS reported to...
Chapter 6
Figure 6.1
Biotransformation pathway of FTOH-based...
Figure 6.2
Occurrence of PFASs in the...
Figure 6.3
Collision-induced dissociation (CID) mass...
Figure 6.4
Negative-ion APPI mass spectra...
Figure 6.5
Smartphone app-based sensor for...
Chapter 7
Figure 7.1
General chemical structure of some...
Figure 7.2
Phthalate metabolites pathway (A); structure...
Chapter 9
Figure 9.1
The redox states of halobenzoquinones.
Chapter 10
Figure 10.1
Scheme of the most commonly...
List of Tables
Chapter 1
Table 1.1
Overview of analytical methods...
Table 1.2
Overview of analytical methods...
Table 1.3
Overview of analytical methods...
Table 1.4
Overview of analytical methods...
Chapter 2
Table 2.1
Pharmaceuticals and their selected...
Table 2.2
Exemplary extraction/clean-up...
Table 2.3
GC/MS application for...
Table 2.4
LC/MS application for...
Chapter 3
Table 3.1
Analytical methods for UV...
Table 3.2
Analytical methods for preservatives...
Table 3.3
Analytical methods for plasticizers...
Table 3.4
Analytical methods for fragrance...
Chapter 4
Table 4.1
NPS categories present in...
Table 4.2
Summary of different analytical...
Table 4.3
Analytical methods used for...
Chapter 5
Table 5.1
Structure and physicochemical properties...
Table 5.2
NORMAN lowest PNECs for...
Table 5.3
Occurrence data of ASs...
Table 5.4
Most frequently used SPE...
Table 5.5
Stationary and mobile phases...
Table 5.6
MRM transitions of AS...
Table 5.7
Figures of merit of...
Chapter 6
Table 6.1
List of poly- and...
Table 6.2
Characteristics of poly- and...
Chapter 7
Table 7.1
Examples of HPVCs and...
Table 7.2
Overview of analytical methods...
Table 7.3
Analytical methods to determine...
Table 7.4
Analytical methods to determine...
Table 7.5
Overview of analytical methods...
Table 7.6
Overview of analytical methods...
Chapter 8
Table 8.1
Classification and physicochemical properties...
Table 8.2
Overview of analytical methods...
Table 8.3
Overview of analytical methods...
Chapter 9
Table 9.1
Main physical-chemical properties...
Table 9.2
Main physical-chemical properties...
Table 9.3
Main physical-chemical properties...
Table 9.4
Main physical-chemical properties...
Table 9.5
Main physical-chemical properties...
Table 9.6
Main physical-chemical properties...
Table 9.7
Main physical-chemical properties...
Table 9.8
Main physical-chemical properties...
Table 9.9
Parametric (*) and guideline values...
Table 9.10
Parametric (*) and guideline values...
Table 9.11
Columns and conditions used...
Table 9.12
Columns and conditions used...
Table 9.13
Columns and conditions for...
Table 9.14
Columns and conditions used...
Table 9.15
Limit of detection of...
Chapter 10
Table 10.1
Average items detected in...
Guide
Cover
Title page
Copyright
Contributors
Preface
Table of Contents
Begin Reading
Index
End User License Agreement
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Contributors
Joshua M. AllenDepartment of ChemistryHigh Point UniversityNorth Carolina, USA
Esteban AlonsoDepartamento de Química AnalíticaUniversidad de SevillaSevilla, Spain
Irene AparicioDepartamento de Química AnalíticaUniversidad de SevillaSevilla, Spain
Anna Białk-BielińskaDepartment of Environmental AnalysisUniversity of GdanskGdansk, Poland
Francesc BorrullDepartment of Analytical Chemistry andOrganic ChemistryUniversitat Rovira i VirgiliTarragona, Spain
Magda CabanDepartment of Environmental AnalysisUniversity of GdanskGdansk, Poland
Julian CampoDesertification Research Center (CIDE)Environmental and Food Safety ResearchUniversity of ValenciaMoncada, Valencia, Spain
Sara CastiglioniDepartment of Environmental HealthScienceIstituto di Ricerche Farmacologiche MarioNegri – IRCCSMilan, Italy
Óscar CastroDepartment of Analytical Chemistry andOrganic ChemistryUniversitat Rovira i VirgiliTarragona, Spain
Maria CeleiroDepartment of Analytical ChemistryNutrition and Food ScienceUniversidade de Santiago de CompostelaSantiago de Compostela, Spain
Amy A. CuthbertsonDepartment of Civil and EnvironmentalEngineeringUniversity of CaliforniaBerkeley, CA, USA
Thierry DagnacAgronomic and Agrarian Research Centre(AGACAL-CIAM)Unit of Organic ContaminantsA Coruña, Spain
Irene DomínguezDepartment of Chemistry and PhysicsUniversity of AlmeriaAlmeria, Spain
María José FarréCatalan Institute for Water Research(ICRA)University of GironaGirona, Spain
Marinella FarréDepartment of Environmental ChemistryInstitute of Environmental Assessmentand Water Research (IDAEA)-CSICBarcelona, Spain
Núria FontanalsDepartment of Analytical Chemistry andOrganic ChemistryUniversitat Rovira i VirgiliTarragona, Spain
Antonia Garrido FrenichDepartment of Chemistry and PhysicsUniversity of AlmeriaAlmeria, Spain
Georgios GkotsisDepartment of ChemistryNational and KapodistrianUniversity of Athens Athens, Greece
Susana Y. KimuraDepartment of ChemistryUniversity of CalgaryCalgary, AB, Canada
Hanna LisDepartment of Environmental AnalysisUniversity of GdanskGdansk, Poland
Maria LlompartDepartment of Analytical Chemistry,Nutrition and Food ScienceUniversidade de Santiago de CompostelaSantiago de Compostela, Spain
Marta LlorcaDepartment of Environmental ChemistryInstitute of Environmental Assessmentand Water Research (IDAEA)-CSICBarcelona, Spain
Rosalía López RuizDepartment of Chemistry and PhysicsUniversity of AlmeriaAlmeria, Spain
Rosa Maria MarcéDepartment of Analytical Chemistry andOrganic ChemistryUniversitat Rovira i VirgiliTarragona, Spain
Julia MartínDepartamento de Química AnalíticaUniversidad de SevillaSevilla, Spain
Maria-Christina NikaDepartment of ChemistryNational and KapodistrianUniversity of AthensAthens, Greece
Monika PaszkiewiczDepartment of Environmental AnalysisUniversity of GdanskGdansk, Poland
Yolanda PicóDesertification Research Center (CIDE)Environmental and Food Safety ResearchUniversity of ValenciaMoncada, Valencia, Spain
Eva PocurullDepartment of Analytical Chemistry andOrganic ChemistryUniversitat Rovira i VirgiliTarragona, Spain
Cristina PostigoDepartment of Environmental ChemistryInstitute of Environmental Assessmentand Water Research (IDAEA)-CSICBarcelona, Spain
Roberto Romero GonzálezDepartment of Chemistry and PhysicsUniversity of AlmeriaAlmeria, Spain
Noelia Salgueiro-GonzálezDepartment of Environmental HealthScienceIstituto di Ricerche Farmacologiche MarioNegri – IRCCSMilan, Italy
Juan Luis SantosDepartamento de Química AnalíticaEscuela Politécnica SuperiorUniversidad de SevillaSevilla, Spain
Piotr StepnowskiDepartment of Environmental AnalysisUniversity of GdanskGdansk, Poland
Nikolaos S. ThomaidisDepartment of ChemistryNational and Kapodistrian University ofAthensAthens, Greece
Konstatinos VasilatosDepartment of ChemistryNational and Kapodistrian University ofAthensAthens, Greece
Ettore ZuccatoDepartment of Environmental HealthScienceIstituto di Ricerche Farmacologiche MarioNegri – IRCCSMilan, Italy
Preface
The occurrence of organic compounds of emerging concern (CECs) in the environment has given rise to growing unease. Although most CECs have been present in the environment for years, some of them have only recently been identified. Thus, some of these compounds remain unregulated and their toxicity and risk unstudied. They occur in different environmental compartments at trace levels (low ppb or ppt). Moreover, CECs belong to different families with several origins and have a broad range of physical-chemical properties. To respond to this situation, sensitive and selective analytical methods have been developed to determine different types of CECs in a broad range of environmental samples. Most of these analytical methods comprise sample preparation followed by chromatographic separation coupled to mass spectrometry. The specific requirements at each step of the analytical method are linked to the properties of the contaminants and sample matrix.
The aim of this book was to compile the analytical methods available to determine CECs in environmental samples. It is organized by families of CECs, with each chapter presenting complete information for each family. The chapters are dedicated to the following families of CECs: pesticides (Chapter 1); pharmaceuticals (Chapter 2); personal care products (Chapter 3); novel psychoactive substances (Chapter 4); artificial sweeteners (Chapter 5); perfluorinated substances (Chapter 6); high production volume chemicals (Chapter 7); musk fragrances (Chapter 8); disinfection byproducts (Chapter 9); and microplastics (Chapter 10). The relevant environmental samples are covered in each chapter (i.e., family of CECs): different types of water (drinking, tap, surface, and sewage), solids (sediment, soil, sludge, dust, as well as biota), and atmospheric samples (air and particulate matter). With a few exceptions, the content of each chapter is organized into the same sections – an overview, sample preparation and collection, determination, and future directions. In each chapter, different analytical methods are proposed through examples of cutting-edge research studies that are summarized in the form of tables to provide an overview of the state of the art; however, the common methods currently employed are also described so that the reader can identify the methods typically used. Thus, this book provides a detailed description of the different approaches for determining each group of CECs in environmental samples with distinctive, critical information about the state of the art for their determination in the environment. The editors truly hope that this book will serve to help researchers, industrial experts, students, decision-makers, and interested members of society learn about the approaches available to monitor each family of CECs, covering most of the CECs occurring in the environment.
We would like to acknowledge the authors for their invaluable contributions. All of the authors of this book are experts and skilled professionals in environmental trace analysis and, in particular, in each of the families of CECs addressed in each specific chapter. Without their effort and dedication, this book would have not been possible. We also sincerely thank our readers for their interest in this book. Thanks for reading and we hope you enjoy it!Núria Fontanals and Rosa Maria MarcéOctober 2021
1 Pesticides
Irene Domínguez, Rosalía López Ruiz, Antonia Garrido Frenich, and Roberto Romero González
Department of Chemistry and Physics, Andalusian Center for the Assessment and Monitoring of GlobalChange (CAESCG), University of Almeria, Agrifood Campus of International Excellence, Almeria, Spain
1.1 Overview of Pesticides
There are thousands of chemicals that can enter the environment and pesticides are among the most significant. They have been used in the last decades in several areas, but agricultural activity is the main source of the impact of pesticides in the environment and therefore they can be present in soil, water, crops as well as in the atmosphere [1].
1.1.1 Properties
Pesticides are a class of chemicals used to limit, inhibit or prevent the growth of harmful animals, insects, weeds or fungi [2]. They can be classified according to different criteria, such as target organism, origin or chemical structure, but the most common is considering the target organism, being herbicides, fungicides, insecticides, etc., among others [3]. There are more than 800 active components and they are available in different accessible products [4]. Despite the benefits of the use of these compounds, they can be toxic to humans and many of them have been classified as endocrine disruptors, and carcinogenic effects have also been reported [5].
The widespread use of pesticides in combination with their physico-chemical properties, such as water solubility, octanol/water partition coefficient, volatility and stability against degradation by abiotic and biotic factors, are the reasons for their distribution and occurrence in different environmental matrices such as water, soil, air and biota [6] by physical processes as sedimentation leaching, sorption and volatilization.
Once pesticides are in the environment, they can be transformed by biotic or abiotic process [7], increasing the number of potential transformation products (TPs) that can be detected, and most of them are still unknown [8]. In this sense, TPs could also have environmental concern and so in addition to the parent compounds they should also be monitored in order to get a comprehensive overview of the environmental fate of pesticides.
1.1.2 Legislation
The presence of these pollutants poses a potential risk for the environment and human health and, therefore, international organizations have set legal limits regarding the presence of pesticides in water and other environmental matrices, for controlling and preventing contamination of environmental ecosystems.
For instance, in Europe, the Water Framework Directive (WFD) is intended to protect transitional waters, inland surface waters, coastal waters and groundwater. Strategies against the chemical pollution of surface waters led to the Directive 2008/105/EC [9], establishing concentration limits of 33 priority substances and 8 other pollutants, including some pesticides such as simazine and trifluralin. Priority substances are considered to pose a significant risk to or via the aquatic environment, so environmental quality standards (EQSs) were set for each of them. Then, amending Directive 2013/39/EU [10] introduced 12 new compounds to the list and the need to establish an additional list of potential water pollutants (Watch List) that should be carefully monitored to support future reviews of the priority substances list. Currently, among the priority substances are 24 pesticides with Annual Average EQS (AA-EQS) values ranging from 1 × 10−8 µg l−1 for heptachlor and heptachlor epoxide to 1 µg l−1 for simazine. In 2020, the European Union (EU) established a new Watch List of substances, including azole compounds and providing maximum acceptable method detection limits for them from 29 to 199 ng l−1 [11]. Additionally, the Drinking Water Directive 98/83/EC, amended by EU 2015/1787 [12], set special quality requirements for water for human consumption. It set concentration limits for a range of hazardous substances, including pesticides, establishing a general maximum individual concentration of 0.1 µg l−1 for individual pesticides (0.030 µg l−1 in the case of aldrin, dieldrin, heptachlor and heptachlor epoxide) and 0.5 µg l−1 for the sum of all individual pesticides and relevant metabolites/TPs detected. The same values, 0.1 and 0.5 µg l−1, for individual and total pesticides respectively, are established as groundwater quality standards in Directive 2006/118/EC [13] on the protection of groundwater against pollution and deterioration.
In the same way, the Clean Water Act (CWA) in the United States (US) establishes the basic structure for regulating quality standards for surface waters discharges of pollutants into the waters. In addition, the Safe Drinking Water Act (SDWA) was aimed at protecting drinking water and its sources (rivers, lakes, reservoirs, springs and groundwater wells). SDWA authorizes the US Environmental Protection Agency (US EPA) to set national health-based standards for drinking water to protect against contaminants, such as pesticides, that may be found in drinking water [14–16]. In this case, the proposed substance priority list is based on a combination of their frequency, toxicity and potential for human exposure at National Priorities List (NPL) sites, setting criterion maximum concentration (CMC) values for each of the pollutants listed. Aldrin, dieldrin, heptachlor and heptachlor epoxide show the lowest CMC values, between 7.7 × 10−7 and 3.2 × 10−5 µg l−1.
Whereas different countries have set pesticide regulation in water matrices, regulation in soils is scarce. For instance, Spain set generic reference levels for a limited number of substances (< 60), some of them considered as persistent organic contaminants, such as dichloro-diphenyl-trichloroethane (DDT) or dichloro-diphenyl-dichloroethane (DDE), whose reference levels were 0.2 mg kg−1 and 0.6 mg kg−1 respectively [17]. These reference levels, in terms of human protection, are the maximum concentration of a substance in the soil that guarantee that contamination does not pose an unacceptable risk to humans. In addition to complying with generic reference levels, it is necessary to determine through toxicological tests that these substances do not present a serious risk to the ecosystem.
1.1.3 Reported or Potential Metabolites and/or Transformation Products
Pesticides in the environment may experience different chemical reactions, leading to the appearance of TPs and metabolites. These compounds have potentially harmful impacts on organisms, even more than their precursors [18], making their monitoring essential. However, because of the great variety of TPs, it is difficult to carry out a comprehensive analysis of their presence, and in consequence, a risk assessment evaluation.
The metabolic/transformation pathways of pesticides can be affected by biological or/and physico-chemical factors in the environment [19]. Hydrolysis is an important degradation mode of pesticides; however, multiple TPs may be produced from different processes, even after hydrolysis [20, 21].
It was noted that the number of substances that must be considered for environmental risk significantly multiplied by a factor of 7.5, just when the precursor compounds were subjected to a photolysis process [22]. This has been observed for terbutryn, mecoprop, penconazole, boscalid diuron and octhilinone pesticides in Figure 1.1, where the number of compounds that should be monitored in environmental samples considerably increase because of the presence of TPs. After evaluating genotoxicity of the proposed TPs, it was suggested that the number of substances that pose a risk onto the aquatic environment increased by a factor of >4. This fact, together with the high incidence of TPs and metabolites in natural waters, constitutes a major concern that needs to be addressed from an analytical and legislative point of view.
Figure 1.1 Forty-five TPs originating from six pesticidal parent compounds. Illustration of the multiplication of known substances that should be further investigates by an environmental risk assessment. Source [22]. Reproduced with permission of Elsevier B.V.
Several studies have revealed the presence of TPs and metabolites in waters at higher concentrations than the parent compounds [23, 24]. The physico-chemical properties (higher mobility and polarity) of the TPs and metabolites might facilitate the migration between surface water and groundwater. Since groundwater is the greatest source of freshwater in the world, the occurrence of some relevant metabolites and/or TPs led to the restriction in the use of certain pesticides, as was recently the case for chlorothalonil and previously simazine and atrazine, among others. Most of the TPs/metabolites found in natural waters are related to acetanilide and triazine herbicides [25]. Such is the case for ethanesulfonic acid (ESA) and oxanilic acid (OA), degradation products of alachlor, metolachlor, as well as acetochlor, and atrazine-desethyl (DEA), atrazine-desisopropyl (DIA), terbumeton-desethyl (TED), terbuthylazine-desethyl (TD) and terbuthylazine-2-hydroxy (T2H). Different analysis has also revealed the occurrence of 2,6-dichlorobenzamide (BAM) from dichlobenil, aminomethyl phosphonic acid (AMPA) from glyphosate, desphenyl chloridazon and methyldesphenyl chloridazon from the herbicide chloridazon and N,N-dimethylsulfamide (DMS) formed from the fungicide tolylfluanid [23, 25–27].
Metabolites were also detected in soils, especially when dissipation studies have been carried out. For instance, nine metabolites of famoxadone were detected in soil samples [28], with IN-JS940 the metabolite detected at the highest percentage in relation to the parent compound, as can be observed in Figure 1.2. Therefore, risk assessment is needed to evaluate potential hazards to the fauna and flora. Tiwari et al. [29] evaluated the presence of endosulfan and chlorpyrifos metabolites in soils because of the higher toxicity of some of these compounds as chlorpyrifos oxon. They determined that metabolite concentrations increased throughout the study when the concentration of the parent molecule decreased. Moreover, it was observed that concentration of metabolites was higher in soil matrices than in water. In the same way, when 2,4-dichlorophenoxyacetic acid (2,4-D) is applied on crops or on soil, it will undergo chemical, biological and physical degradation processes depending on the environmental factors, which will determine the metabolites formed. For example, 2,4-D DMA (2,4-D dimethylamine salts) is dissociated to 2,4-D acid after its application on the soil [30], so in addition to the parent compound, different TPs should be monitored.
Figure 1.2 Metabolite behavior according to the concentration of famoxadone during monitoring period (100 day) for soil experiments at: (a) normal dose (2.4 mg g−1 soil) and (b) double dose (4.8 mg g−1 soil). Source [28]. Reproduced with permission of Elsevier B.V.
1.1.4 Occurrence in the Environment
Pesticides and their TPs/metabolites are widely distributed in the environment and they can be detected in water, soil, sediments, aquatic biota and air [31], as can be observed in Figure 1.3, because of surface runoff from arable lands, leaching from drainage systems, volatilization, etc. They can have toxic effects in population living close to these areas [32]. For instance, when pesticides are applied in agricultural areas, approximately 20–30% of the amount is lost due to the spray drift process, whereas another significant fraction is placed into the soil or surface waters [33].
Figure 1.3 Neonicotinoid insecticides in the environment: sources, pathways, receptors and related process. Source [31]. Reproduced with permission of Elsevier B.V.
Pesticides have been widely detected in the aquatic media. Several scientific papers and technical reports have revealed the presence of pesticides in surface water, groundwater, drinking water as well as treated wastewater which is intended to be discharged in surface waters [34].
In 2018 the European Environment Agency (EEA) indicated that chemical status of surface waters, related to pesticides, has improved between the 1st and 2nd River Basin Management Plants (RBMPs) assessments [35]. However, pesticides listed as priority substances were still detected. Among them, isoproturon and hexachlorocyclohexane were the most frequently reported, followed by endosulfan and chlorpyrifos. Furthermore, the presence of pesticides in groundwater is a failure to achieve good chemical status. As reported by EAA, several groundwater bodies exceed the permitted concentrations set by EU of total pesticides, as well as the level set for desethylatrazine, atrazine and simazine.
Herbicides such as atrazine and fungicides such as metalaxyl have been detected in aquifers for drinking water in US [25]. The most found pesticide in drinking water in Ireland was 2-methyl-4-chlorophenoxyacetic acid (MCPA), widely used for rush control in grassland [36].
A recent study in The Netherlands, intended to assess the occurrence of pesticides in ground and surface water used as drinking water sources, has revealed the detection of 15 recently authorized pesticides, such as fluopyram and thiamethoxam, which demonstrates the importance of keeping routine monitoring methods [36].
Non-agricultural uses of pesticides are also common in urban environments, such as indoor uses or applications in gardens, roads and sealed areas, among others. As a result, triazine herbicides (atrazine, simazine and prometon) and organophosphate insecticides (chlorpyriphos and diazinon) are frequently detected in U.S. urban surface waters [34].
Pesticide occurrence in soils was inversely related to the occurrence in surface water, and one of the main factors is the hydrophobicity of the compounds, expressed by the n-octanol/water partition coefficient (Kow). Thus, pesticides with log Kow > 3 were more detectable in soils than in water. In a study performed in Argentine ecosystem, it was observed that the most detected herbicide residues (>30% of detection frequency) were acetochlor, atrazine and its metabolite (hydroxyatrazine), flurochloridone, glyphosate and its metabolite (aminomethylphosphonic acid, AMPA) and metolachlor, whereas the most frequently detected insecticides were chlorpyrifos and imidacloprid [37]. In this study, glyphosate and its metabolite AMPA were also found in all the environmental samples (soil, sediments and surface water), detecting AMPA up to 713 mg kg−1, glyphosate at 32 mg kg−1 and 5 mg l−1 in sediments and water respectively.
Another group of pesticides really known for their persistence are 2,4-D-based herbicides. The two chlorine that are present in their molecules confers persistence with an estimate half-life between 7 and 312 days, which depends on the environmental conditions [38]. Several studies have reported the presence of 2,4-D and derivates in the environment because of different activities, such as agricultural activities and rain and irrigation water. Discharges from manufacturing plants, leaching and accidental spills [39] represent an important source of the aforementioned herbicide.
The key properties that determine the presence of pesticides and their accumulation in biota are hydrophobicity and persistence. Thus, if water solubility is <1 mg l−1 or log Kow is >3, they have the potential to accumulate in biota and it may be an indicator of contamination [40]. For instance, earthworms are used as indicators to the response of pesticides [41], but fish are considered as major reservoirs of pesticides and their concentration in fish tissues has been used as an indicator of bioaccumulation [42]. High concentrations of organochlorine pesticides (OCPs) have been found in fish tissues from aquatic environments in Africa [43], detecting DDTs, lindane, mirex and endosulfan at concentrations up to 100 µg kg−1. Other studies, developed in South-America (southeastern Brazil and the coast of the Argentinean Pampas), showed that lindane and endosulfan levels could cause long-term or short-term damage to biota [44]. Additionally, it was observed that OCPs were highly bioaccumulated in soil mesofauna (up to 260 µg g−1) [45].
In the last years, several river basins were monitored in the Iberian Peninsula, and in addition to water and sediment, biota was also analyzed. Thus, 50 pesticides were monitored in Guadalquivir river basin, but none of them were detected in biota, although there were detected in water and sediments, especially organophosphorus and triazines at concentrations up to 13 ng l−1 in water and 13.2 ng g−1 dry weight (dw) in sediment [46]. However, azinphos-ethyl, chlorpyriphos, diazinon, dimethoate and ethion were detected in different species of fish from Jucar river basin, observing that the maximum average concentration was found in European eels (up to 0.024 ng kg−1), whereas in water, dichlofenthion, imazalil pyriproxyfen and prochloraz, commonly used in farming activities, were mainly detected [47]. In biota from Llobregat river basin, chlorpyrifos and azinphos-ethyl were detected at 44.75 ng g−1 dw and 105.81 ng g−1 dw, indicating possible bioaccumulation. Nevertheless, authors concluded that these values do not represent a high risk to biota. On the other hand, triazines, organophosphorus and neonicotinoids were mainly detected in water, at concentrations >600 ng l−1, as can be observed in Figure 1.4, with chlorpyrifos the compound most widely detected in soils, at concentrations up to 130 ng g−1 dw [48]. Additionally, the Ebro river basin was also monitored, detecting imazalil and diuron at the highest concentrations in water (410 and 150 ng l−1 respectively), chlorpyrifos, diazinon and diclofenthion in sediments, whereas the only compound detected in biota was chlorpyrifos, which was detected at concentrations up to 840.2 ng g−1 [49].
Figure 1.4 Pesticide families detected in (A) water, (B) sediment and (C) fish samples from Llobregat basin in 2010 and 2011 according to the sampling point. Source [48]. Reproduced with permission of Elsevier B.V.
The presence of pesticides in air depends on the specific agricultural areas, as well as those pesticides that can be transported from nearby places, observing a relationship between the concentration of some of the compounds detected in air and diseases and mortality [50].
Several studies were performed to monitor the presence of pesticides in outdoor and indoor air [51], bearing in mind that volatile pesticides, such as OCPs, can largely remain in the atmosphere after volatilizing from contaminated soils and water. For instance, p,p’-DDT and p,p’-DDD were detected in African air at concentrations of 47 pg m−3 and 12 pg m−3 respectively, whereas other compounds as dieldrin, hexachlorobenzene (HCB), aldrin, lindane and chlordane were also detected but at lower concentrations [52].
In a study developed in Vietnam, 452 pesticides were included in a database, detecting 18 (12 insecticides, 4 herbicides and 2 fungicides) in the collected air samples, and the total concentration ranged from 3.35 to 89.0 ng m−3, with the most detected pesticides being permethrin, carbofuran, fenobucarb and chlorpyrifos as well as metolachlor [53]. Some prohibited pesticides in the EU, such as chlorpyrifos, permethrin, deltamethrin, cypermethrin and carbofuran, were also detected [53]. In the same country, 26 pesticides (13 pesticides, 7 fungicides and 6 herbicides) were detected in the air samples, at higher concentrations, ranging from 43 to 370 ng m−3. Permethrins, chlorpyrifos and propiconazole were detected and this may result from their widespread use for both agricultural and domestic purposes in rural areas [54].
Due to their high persistence, OCPs were monitored in addition to current-use pesticides (CUPs) in two National Parks in the Rio de Janeiro State. The highest concentrations of endosulfan (up to 3202 pg m−3), cypermethrin (881 pg m−3) and chlorpyrifos (270 pg m−3) indicated background air levels of OCPs. On the other hand, CUPs seemed to behave like pseudo-persistent organic pollutants (POPs) although it was believed that they are not persistent in the environment [55].
In another study, carbendazim, metalaxyl, myclobutanil and terbuthylazine were detected in air from rural areas of Valencia (Spain) at concentrations ranging from 16 to 174 pg m−3 [56].
Bearing in mind that pesticides can easily adhere to the particulate matter, they have also been analyzed in this matter. Thus, 40 CUPs were determined in PM10 of Valencia Region (Spain) observing that omethoate was detected at the highest average level (141 pg m−3) [57]. A similar study was performed in the “Todos los Santos Bay” region (Brazil), where 13 pesticides were analyzed in PM2.5 samples, and concentrations ranged from 20 to 315 pg m−3, being carbofuran, malathion and permethrin, the compound most widely detected [58].
1.2 Sample Preparation and Collection
In order to ensure accurate pesticide determination in environmental samples, sample collection and preparation should be carefully designed to minimize potential errors during these steps and therefore error propagation will be limited.
1.2.1 Protocols for Collecting and Preparing Samples
Sample collection is critical to get representative samples as well as to avoid any modification of the initial chemical composition of the sample.
For instance, a guidance on sampling water techniques can be found in the ISO Standard on Water Quality – Sampling 5667. The selection of sampling point, which should cover the area of surveillance, must be subject to local conditions, such as water homogeneity and vertical and lateral mixing.
The sample containers as well as transport and storage arrangements should not lead to changes in the relevant chemical status. Therefore, according to sampling for synthetic organic compounds, water samples must be stored in glass, polytetrafluoroethylene (PTFE) or stainless-steel containers, and they should be analyzed within 24 hours and stored in the dark at 1–5°C.
On the other hand, the development and application of passive sampling techniques are highly recommended [59]. Those techniques allow for the accumulation of pesticides by passive diffusion onto a liquid or solid absorbent showing affinity for a certain type of substance. The semipermeable membrane device (SPMD) and the polar organic chemical integrative sampler (POCIS) are the most common passive samplers for organic pollutants. SPMD based on triolein sorbent can be applied for neutral organic chemicals with a log Kow > 3 (lipophilic pesticides), while POCIS, which uses Oasis HLB phase, is intended for the sorption of more water-soluble organic chemicals with Kow < 3 (polar pesticides). To ensure the monitoring of a high number of pollutants, different types of passive samplers could be used together [6]. In this sense, an interlaboratory study on passive sampling of emerging water pollutants showed low interlaboratory variability in the analysis of replicate samplers when POCIS was used for the monitoring of 7 polar pesticides. The same study established a series of recommendations to take into consideration, especially when passive samplers are combined with liquid chromatographic-mass spectrometric (LC-MS) methods [60].
In the same way, soil samples should be collected from growing fields using a grid pattern uniformly distributed. For instance, a 3 × 3 grid is commonly used for smaller fields, whereas 5 × 5 or even larger grids are used for very large fields and a “W” or “Z” pattern is commonly used. Each sample site represents one portion of the total sample, and then a composite sample can be formed, ensuring homogeneity. Normally, samples are collected at a 15 cm depth. Moreover, additional steps such as removing litter, plant roots and big stones from the soil samples could be needed [61] and sometimes soils should be dried with [62] or without heat [63], homogenized and finally stored at −18°C until analysis [64]. Finally, an exhaustive characterization of the soils according to several parameters, such as pH, percentage of organic matter, carbon monoxide, sand, silt, clay and grit [28, 65], is advisable to provide useful information and set a relationship between pesticide presence and physico-chemical characteristics of the soil.
In relation to air sampling, other important criteria should be considered as materials do not react with target compounds; it must be located in a place where free air masses can reach; the sampler should be protected from rainfall, dust or other sources of contamination as well as requiring low maintenance [33]. Furthermore, it should be planned bearing in mind whether only gas phase, particulate matter or both of them are going to be collected, among other factors.
Finally, for biota sampling, special care should be taken with small biota samples, which are more sensitive to contamination, and degradation of loss of analytes. Long-term storage should be performed in darkness and low temperature, and before sample treatment, dry or wet homogenization is needed [66].
1.2.2 Sample Extraction and Clean-up
For the monitoring of ultra-trace levels of pesticides in water, extraction and concentration steps are required prior to the analytical determination. Liquid-liquid extraction (LLE) allows for the detection of a large range of non-polar pesticides while requiring minimal instrumentation, being at the same time both a simple and a precise technique. Although less and less, this technique is still used for the extraction of pesticides from water samples prior to gas chromatography (GC) analysis [67, 68]. However, one major drawback is the large solvent volumes, usually dichloromethane, required in LLE. Therefore, solid phase extraction (SPE) has become the most common extraction technique [69]. Indeed, it is the most powerful sampling and enrichment approach for complex mixtures of known and unknown contaminants, and different sorbent phases can be used, allowing for the extraction of a wide range of pesticides with different physico-chemical properties.
As shown in Table 1.1, the polymeric reversed phase sorbent, Oasis HLB, is commonly used for the extraction of pesticides in water samples providing quantitative recoveries in most cases [18, 23, 70–72]. Furthermore, other sorbents have been successfully applied for the analysis of pesticides and their TPs in natural waters, such as a mixture of hydrophilic–lipophilic balance, weak anion and cation exchange sorbents (2 : 1 : 1, w/w/w) [73], and Strata-X reversed in combination with the mixture of Strata-X mixed-mode (AW and CW) and Isolute ENV + [74].
On-site integrated large-volume SPE has also been proven to be a promising tool for the monitoring of pollutants, including pesticides, in water sources [75]. On the other hand, the possibility of using on-line SPE systems allows for minimizing sample manipulation and cross-contaminations as well as improving sample throughput [76]. Hence the development of fully automated methods, based on the combination of on-line SPE and LC-MS, has been given much attention in the last few years, being applied for the monitoring of ca. 100 pesticides in natural and drinking waters [24, 77], as well as 51 pesticides, covering highly polar compounds, in surface and groundwaters [78].
Simple and miniaturized sample preparation techniques have been considered in recent years as optimal alternatives [79]. Among them, solid phase microextraction (SPME) is the most used technique, although the application of QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe)-based protocols [21, 80], stir bar sorptive extraction (SBSE) [77], as well as liquid-phase microextraction (LPME) [81, 82], has also been suitable for the extraction of pesticides from water matrices.
SPME is a simple, sensitive, rapid and solvent-free technique in which the organic compounds are adsorbed/absorbed (depending on fiber coating) directly from the aqueous sample into the fiber and then thermally desorbed at the injection port of the GC, considerably simplifying the analysis procedure. In this sense, the availability of SPME devices in latest GC equipment leads to the complete automatization of the analytical process, allowing for improving data quality, the productivity of staff and instruments, and increasing the sample throughput [83]. This has been demonstrated in recent methodologies involving the on-line combination of SPME and GC coupled to high-resolution mass spectrometry (HRMS) allowing for the determination of priority substances, including pesticides, in surface and wastewaters [84, 85] providing limits of quantification (LOQs) at ng l−1 levels. Novel SPME sorbents, such as magnetic deep eutectic solvent (DES)-based polymeric hydrogel [86] and carbon nanomaterials [87, 88], have been successfully applied for the monitoring of pesticides in different water resources as can be seen in Table 1.1.
On the other hand, vacuum-assisted evaporative concentration has been effective for the monitoring of organic micropollutants [89], including pesticides such as chlorothalonil and TPs (sulphonic acids and phenols) by LC-Orbitrap-MS [90]. However, sometimes these extraction procedures are avoided, and direct injection of water samples, after filtration, can be considered when using LC. In fact, its combination with tandem MS (MS/MS) has allowed for the determination of pesticides at ultra-trace levels in surface and groundwaters [25, 27, 91].
Table 1.1 Overview of analytical methods applied to monitor pesticides in environmental waters.a
Pesticides
Matrix
Extraction technique
Determination technique
Recovery (%)
LOQ (µg l
−1
)
Reference
4 OCP and 2 OPPs
Surface water
LLE (dichloromethane)
GC-FID
80–90
0.002
[
68
]
296 pesticides + 156 pharmaceuticals, 18 consumer products, 10 industrial chemicals and 4 others
Coastal waters
SPE (Oasis HLB and SpePak cartridges)
LC-QTOF-MS
70–130
0.00002–0.300
b
[
70
]
14 pesticides and TPs
Surface water
and drinking water
SPE (Oasis HLB cartridge)
UHPLC-QTrap-MS/MS
85–105
0.01–0.1
[
71
]
19 acidic herbicides + metabolites
River water
SPE (Oasis HLB cartridge)
LC-QqQ-MS/MS
64–111
0.004–0.022
[
72
]
6 neonicotinoids and metabolites
Drinking water
SPE (Oasis HLB cartridge)
LC-DAD-QqQ-MS/MS
& QTOF-MS
57–120
0.000057–0.000488
b
[
18
]
ca. 500 pesticides and TPs
Surface water and groundwater
SPE (Oasis HLB cartridge)
UHPLC-QTOF-MS
—
—
[
23
]
8 pesticides + TPs
Surface water
Mix mode SPE:
(HLB: WAX: WCX, 2 : 1: 1)
LC-QqQ-MS/MS
43–141
0.00002–0.0056
b
[
73
]
125 pesticides and metabolites + 130 pharmaceuticals and metabolites + 42 antibiotics and metabolites + 63 others
Surface and marine water
SPE (Strata-X and the mixture Strata-X-AW: Strata-X-CW: Isolute ENV + (1 : 1 : 1.5))
LC-LTQ-Orbitrap-MS
83–93
—
[
74
]
251 contaminants (pesticides, pharmaceuticals or industrial chemicals and their transformation products)
Surface water
Onsite integrative large-volume SPE (HR-X sorbent)
UHPLC-LTQ-Orbitrap MS
60–123
—
[
75
]
96 including pesticides and TPs
Surface water,
groundwater and drinking water
On-line SPE
UHPLC-QqQ-MS/MS
—
0.005–0.025
[
24
]
51 pesticides
Surface water and groundwater
On-line SPE (Prospekt-2-system)
LC-QqQ-MS/MS
80–125
0.010
[
78
]
8 pesticides
Surface water and groundwater
QuEChERS (Acetonitrile, MgSO
4
and NaCl)
GC-Q-MS
85–103
0.95–13.69
[
80
]
Cyflumetofen + 2 metabolites
Surface water
QuEChERS (Acetonitrile, MgSO
4
and NaCl)
UHPLC-QqQ-MS/MS
79–118
0.7–9.8
[
21
]
102 pesticides
Surface water and groundwater
SBSE (PDMS) (GC)
On-line SPE (LC)
GC-Q-MS (27)
UHPLC-QqQ-MS/MS (75)
—
0.015–0.025 (GC)
0.005–0.025 (LC)
[
77
]
10 pesticides
Surface water
HF-LPME
GC-Q-MS
85–115
0.14–1.69
[
82
]
14 pesticides + 16 PAHs + 26 PCBs + 6 BDEs
Surface water
On-Line SPME (DI, PA fiber)
GC-DFS-HRMS
87–116
0.0001–0.050
[
84
]
16 pesticides
Surface water, marine water and groundwater
Magnetic SPME with a magnetic DES-based polymeric hydrogel
GC-µECD
61–120
0.006–0.399
[
86
]
24 pesticides
Surface water
SPME (Novel carbon nanomaterial sorbent)
GC-Q-MS
70–123
0.0007–3.7320
[
87
]
18 chiral pesticides
Surface water and influent and effluent wastewater
Magnetic SPME (Amino modified multiwalled carbon nanotubes)
LC-QqQ-MS/MS
83–105
0.00035–0.00204
[
88
]
Pesticides
Matrix
Extraction technique
Determination technique
Recovery (%)
LOQ (µg l
−1
)
Reference
Chlorothalonil + 6 TPs
Surface water and groundwater
Vacuum-assisted evaporative concentration
LC-Orbitrap-MS
85–110
0.0002–0.010
[
90
]
215 pesticides and TPs (Method SH2437)
30 pesticides
(Method LC9045)
3 herbicides (glyphosate, AMPA and glufosinate)
(Method GLYPH)
Groundwater
SH2437 &: LC9045: Direct injection
GLYPH: derivatization with FMOC prior to on-line SPE
LC-QqQ-MS/MS
78–114
0.001–1.350b
0.001–0.028b
0.020b
[
25
]
150 pesticide metabolites
Surface water
and groundwater
Direct injection
LC-QqQ-MS/MS
—
0.003–2.000
[
27
]
16 polar pesticides + pharmaceuticals
Groundwater
Extraction from passive sampler (POCIS): acetone:methanol
UHPLC-QqQ-MS/MS
42–116
0.00003–0.00135
b
[
59
]
aAbbreviations: BDEs: Brominated diphenyl ethers; DAD: Diode array detector; DES: Deep eutectic solvent; DFS-HRMS: Magnetic sector high resolution mass spectrometry: DI: Direct injection; FID: Flame ionization detection; FMOC: 9-florenylmethyl-chloroformate; GC: Gas chromatography; HF-LPME: Hollow fiber-liquid phase microextraction; HLB: Hydrophilic-lipophilic balanced; LC: Liquid chromatography; LLE: Liquid-liquid extraction; LOQ: Limit of quantification; LTQ: Linear ion trap; MS: Mass spectrometry; MS/MS: Tandem mass spectrometry; µECD: Micro electron capture detector; OCPs: Organochlorine pesticides; OPPs: Organophosphorus pesticides; PA: Polyacrilate; PAHs: Polycyclic aromatic hydrocarbons; PCBs: Polychlorinated biphenyls; PDMS: Polydimethylsiloxane; POCIS: Polar organic chemical integrative samples; Q: Single quadrupole; QqQ: Triple quadrupole; QTOF: Quadrupole time of flight; QTRAP: Hybrid triple quadrupole-linear ion trap; SBSE: Stir bar sorptive extraction; SPE: Solid phase extraction; SPME: Solid phase microextraction; TPs: Transformation products; UHPLC: Ultra-high-performance liquid chromatography; WAX: Weak anion exchange; WCX: Weak cation exchange.
bLimit of detection.
In relation to solid samples, such as soils, the most common methods were based on solid-liquid extraction (SLE), pressurized liquid extraction (PLE) and QuEChERS (see Table 1.2). In SLE methods, solvent mixtures such as acetonitrile and water have been widely used. For example, a mixture of water/acetonitrile (10 : 90, v/v) was utilized to monitor pesticide residues in soils from Argentina [62], or a mixture of water/acetonitrile (40 : 60, v/v) was used for the extraction of oxanilic and sulfonic acids metabolites [92]. Hu et al. employed methanol:water (50 : 50, v/v) instead of acetonitrile for the extraction of acetochlor and propisochlor in soils from Beijing (China) [63]. Colazzo et al. tested different solvents and mixtures, such as acetonitrile, methanol, water and methanol/water, choosing methanol as the best option (recoveries ranged from 45 to 90%) to determine pesticide residues in paddy fields and sugar cane from Uruguay [93].
Table 1.2 Overview of analytical methods applied to determine pesticides in soil matrices.a
Pesticides
Extraction
Determination technique
Recovery (%)
LOQ (µg kg
−1
)
Reference
Famoxadone and metabolites
SLE: Water/Acetonitrile 1% acetic acid (50 : 50, v/v)
LC-Orbitrap-MS
72–113
20
[
28
]
OCPs, OPPs, pyrethroids (58)
SLE: Water/Acetonitrile 1% acetic acid. Extraction salts: MgSO4 and sodium acetate
Clean-up: MgSO4, PSA & C18
GC-QqQ-MS/MS
69−119
100−5000
[
61
]
30-multicalss
SLE: Methanol
Clean-up: SPE (Oasis HLB)
LC-QTRAP-MS/MS
70−120
1−10
[
93
]
18-multiclass
SLE: Water/Acetonitrile (1 : 5, v/v)
LC-QqQ-MS/MS
50−120
50
[
62
]
Fenamidone, propamocarb
SLE: Methanol or Water
Clean-up: MgSO4 & PSA
LC-QqQ-MS/MS
77−108
0.4–2
[
100
]
Oxanilic and sulfonic acid metabolites of acetochlor
SLE: Acetonitrile /Water (60 : 40, v/v)
LC-QqQ-MS/MS
91−120
1−2
[
92
]
Endosulfan, chlorpyrifos and their metabolites
SLE: Ethyl acetate with a 1 : 5 (w/v) soil-to-solvent ratio
GC-IT-MS
76−95
10−50
b
[
29
]
Acetochlor and Propisochlor
SLE: Methanol/water (1 : 1 v/v)
Clean-up: PSA
GC-ECD
80−116
10
[
63
]
10 OCPs
SLE: Water/Acetonitrile
Clean-up: MgSO4
GC-QqQ-MS/MS
70−115
2−40
[
106
]
10 OCPs and metabolites
QuEChERS.
Clean-up: Sulfuric acid and florisil
GC-IRMS
60−100
500
[
115
]
218
QuEChERS using Acetonitrile 2.5% formic acid. Extraction salts: MgSO
4
& sodium acetate
LC-QqQ-MS/MS
GC-QqQ-MS/MS
70−120
0.5−20
[
99
]
Pydiflumetofen enantiomers
QuEChERS
Clean-up: MgSO4 & C18
UHPLC-QqQ-MS/MS
84–103
5
[
97
]
Pyrethroid pesticide metabolite
QuEChERS
Clean-up: d-SPE
GC-IT-MS
70−94
13
[
64
]
32-multiclass
UAE: 40 mL of methanol–water (4 : 1 v/v). 20 minutes
LC-Q-MS
60−110
1.5−5.0
[
107
]
25-Triazines, phenylureas, phenoxy acid pesticides
PLE: Dichloromethane –acetone (1 : 1, v/v) and Acetonitrile–water (2 : 1, v/v)
LC-QqQ-MS/MS
65−120
0.1−3
[
95
]
51 Fungicides and insecticides
PLE: Methanol:acetonitrile (70 : 30, v/v) Methanol: Acetonitrile:formic acid (65 : 30:5, v/v)
LC-QqQ-MS/MS
57−136
0.3−8.5
[
96
]
9 OPCs & PAHs
MAE: Hexane/water (3 : 2 v/v)
GC-QqQ-MS/MS
−
−
[
104
]
8 Pesticides and metabolites
DLLME
LC-FD
70−120
0.07−80
[
114
]
8 Chiral pesticides
MSPD-DLLME
LC-QqQ-MS/MS
87−104
0.2−1.5
[
65
]
5 OPPs
Deep eutectic solvent embedded sponge
LC-UV-Vis
−
−
[
113
]
aAbbreviations: DLLE: Dispersive liquid-liquid microextraction; d-SPE: Dispersive solid phase extraction; ECD: Electron capture detector; FD: Fluorescence detection; GC: Gas chromatography; HLB: Hydrophilic-lipophilic balanced; IRMS: Isotope ratio mass spectrometry; IT: Ion trap; LC: Liquid chromatography; MAE: Microwave-assisted extraction; MS: Mass spectrometry; MSPD: Matrix solid phase dispersion; MS/MS: Tandem mass spectrometry; OCPs: Organochlorine pesticides; OPPs: Organophosphorus pesticides; PAHs: Polycyclic aromatic hydrocarbons; PCBs: Polychlorinated biphenyls; PLE: Pressurized liquid extraction; PSA: Primary secondary amine; Q: Single quadrupole; QqQ: Triple quadrupole; QTRAP: Hybrid triple quadrupole-linear ion trap; SLE: Solid-liquid extraction; SPE: solid phase extraction. UAE: Ultrasonic-assisted extraction; UHPLC: Ultra-high-performance liquid chromatography; UV-Vis: Ultraviolet-visible detection.
bInstrumental method (µg l−1).
The PLE method is based on the use of a solvent that is applied at high pressure and temperature through a solid or semisolid sample (e.g. soils) to effectively extract the analytes, being faster than conventional SLE. The selection of optimum experimental parameters, such as extraction temperature, flush volume and preheat time, can allow the extraction of a large number of pesticides within a wide polarity range in only one step [94]. Two different extraction solvents, dichloromethane:acetone (1 : 1, v/v) and acetonitrile:water (2 : 1, v/v), were used for the determination of triazines, phenylureas and phenoxy acid pesticides [95]. Fungicides and insecticides were also extracted using PLE, applying two extraction solvents, methanol:acetonitrile (70 : 30, v/v) and methanol:acetonitrile:formic acid (65 : 30:5, v/v), obtaining recoveries from 57% to 136% [96].
The QuEChERS approach has been widely used to extract pesticides from soils [3] and several modifications were carried out to improve sample extraction. One of them was matrix hydration, which consisted of the addition of water before solvent addition [97]. This approach was used for the extraction of pydiflumetofen enantiomers, obtaining recoveries between 84–103% or for the determination of afidopyropen and its metabolite residues in a cotton field with acceptable recoveries (85–100%) [98]. Another modification was the acidification of the solvent to improve the extraction of target analytes. For instance, acetonitrile, acidified with 2.5% formic acid, provided acceptable recoveries (70–120%) for the simultaneous monitoring of 218 pesticide residues in clay loam soil [99]. The clean-up step was not commonly used in soil samples and only a few studies employed dispersive solid phase extraction (d-SPE). The sorbents and salts commonly used were primary secondary amine (PSA) and anhydrous magnesium sulphate (MgSO4) [98, 100]. Other sorbents, such as C18, were also used in combination with PSA [61] or with MgSO4 [97].
Finally, SPE, using OASIS HLB cartridges, was also applied to concentrate the extract before chromatographic analysis [93].
Tissue analysis is more challenging than water or soil analysis due to the complexity of those matrices. Thus, for the extraction of pesticides from biota, different extraction techniques can be applied such as SPME [40], PLE, SPE, ultrasonic-assisted extraction, dispersive liquid-liquid extraction and SBSE [101], adding a freezing-lipid filtration in fatty materials. Other procedures such as QuEChERS have been widely used in the last few years, using in the clean-up step based on d-SPE a mixture of sorbents that includes MgSO4, PSA, C18 and graphitized carbon black (GCB) [46, 47, 49], as indicated in Table 1.3.
Finally, pesticides are usually extracted from air using active or passive samplers (see Table 1.4). The active ones are mainly based on SPE by pumping high volumes of air
