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Editors
Inamuddin Mohd Imran Ahamed
Department of Applied Chemistry, Department of Chemistry, Faculty of Science
Zakir Husain College of Engineering Aligarh Muslim University
and Technology, Faculty of Aligarh, India
Engineering and Technology
Aligarh Muslim University
Aligarh, India

Eric Lichtfouse
CNRS, IRD, INRAE, Coll France,
CEREGE
Aix-Marseille University
Aix-en-Provence, France

ISSN 2210-4410 ISSN 2210-4429 (electronic)

Sustainable Agriculture Reviews
ISBN 978-3-030-54711-0 ISBN 978-3-030-54712-7 (eBook)
https://doi.org/10.1007/978-3-030-54712-7

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland
AG 2021
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Preface

Pesticides play an important role in agriculture by protecting crops against pest

attacks, thus improving the production yield. However, the use of pesticides causes
toxicity to human beings because of their existence as pesticide residues. The main
causes for pesticide residues in food are lack of knowledge regarding pesticide use
and non-strategic agricultural practices to improve crop production. This book
reviews the occurrence of pesticide residues in biotic and abiotic environments.
The topics include pesticide residues present in aquatic animals, food, agriculture,
horticulture, pollen and dairy products. This book will help researchers in academia
and industry to solve critical issues related to pesticide residues.

v
vi Preface

Chapter 1 by Pareja et al. highlights trends in sample preparation approaches and

instrumental techniques for pesticide residues determination in fish. Additionally,
the occurrence of pesticides in fish is addressed. Perspectives in the field of analytical
applications, food safety and environmental surveillance of pesticides in fish are
described. Chapter 2 by González-Curbelo and González-Sálamo provides a critical
vision of the analytical methodologies that have been and are also being currently
applied for the extraction of multiclass pesticides from milk, dairy products and
pollen with particular emphasis on the sample pre-treatment step, which is crucial for
a suitable analytical determination. Chapter 3 by Mondal and Kole deals with
various processes involved in pesticide transportation to the hydro-system. Methods
for determination of multiple pesticides and their residual status in the aquatic
system are discussed. The reason for the occurrence of banned organochlorine
pesticides is explained. Deterministic approaches for risk assessment to aquatic
health and options for management are highlighted. Chapter 4 by Soares at
al. discusses the use of pyrethroid pesticides to control ectoparasites in poultry
that, with an indiscriminate application, can leave residues in the environment and
animal tissues and harm the health of poultry farmers. It also presents safe and clean
new technologies as strategies to replace pesticide use. Chapter 5 by Fernandes et al.
gives a summary of analytical methods for the analysis of pesticide residues in
strawberries. Several sample preparation and chromatographic techniques are
discussed in detail. The focus of the chapter is to show the importance of the
analytical data for food safety and quality. Chapter 6 by Karasali and Pavlidis
discusses the mechanism of formation and the environmental significance of ‘Non-
Extractable Residues’ in soil. The term ‘Bound Residues’ and the new term ‘Non-
Extractable Residues’ are defined and interpreted in different ways. The major focus
is given to their types and the methods used for their identification and quantifica-
tion. Chapter 7 by Sousa et al. addresses the relevance of human biomonitoring of
pyrethroids. 3-phenoxybenzoic acid is a major urinary biomarker for numerous
pyrethroids and most frequently assessed. Studies from different countries and
continents that assess exposure in diverse populations are addressed, and finally,
the different applied analytical methodologies are also discussed. Chapter 8 by Nazir
et al. highlights the different techniques of pesticide contaminants removal from
water. These include carbon nanotubes, graphene, nano-crystalline metal oxides,
hydrogen peroxides, ultrasonic wave, hybrid process, bioremediation, photocatalytic
degradation, adsorption, membrane separation, biopurification systems, composite
material and ion exchange resins. The emphasis is on inexpensive detection, reme-
diation and removal methods. Chapter 9 by Rano and Singh discusses different
methods of pesticide contamination in various food residues and its related negative
health issues. It further describes various chemical methods for the analysis of
pesticide content in food. Different diagnostic methods have also been highlighted
to quantify pesticide ingested via food and its bio-magnification in the body.
Chapter 10 by Puthur et al. discusses the deleterious effects of various pesticides
on the avian fauna inhabiting the wetland ecosystems. Pesticides, specifically organ-
ochlorines, organophosphates and carbamates, induce various hormonal imbalances
and inactivation of enzymes, leading to altered or defective growth responses in
Preface vii

birds, which is summarized in this paper. Chapter 11 by Clasen et al. addresses the
problem of disorderly pesticide use and the risks it may pose to nature and humans.
The methods of pesticide evaluation currently used as well as the occurrence and
effects of different pesticides on aquatic and terrestrial organisms and humans are
presented.

Aligarh, India Inamuddin

Aligarh, India Mohd Imran Ahamed

Aix-en-Provence, France Eric Lichtfouse

Contents

1 Determination of Pesticide Residues in Fish . . . . . . . . . . . . . . . . . . 1

Lucía Pareja, Horacio Heinzen, María Verónica Cesio,
Marcos Colazzo, and Andrés Pérez-Parada
2 Analysis of Pesticide Residues in Pollen and Dairy Products . . . . . . 47
Miguel Ángel González-Curbelo, Javier González-Sálamo,
Diana Angélica Varela-Martínez, and Javier Hernández-Borges
3 Monitoring and Evaluation of Pesticide Residues in Aquatic
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Rahul Mondal and Ramen Kumar Kole
4 Pyrethroid and Residues in Chickens and Poultry Litter . . . . . . . . . 145
Carlos Eduardo Carlos da Silva Soares, Vildes Maria Vildes Scussel,
and Fabiano Fabiano Dahlke
5 Extraction Procedures and Chromatography of Pesticides
Residues in Strawberries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
Virgínia Cruz Fernandes, Luz Maia, Luísa Correia Sá, Sara Sousa,
Paula Paíga, José L. Vera, Valentina F. Domingues,
and Cristina Delerue-Matos
6 Non-extractable Pesticide Residues in Soils . . . . . . . . . . . . . . . . . . . 203
Helen Karasali and George Pavlidis
7 Pyrethroids Metabolites in Human Urine Samples . . . . . . . . . . . . . 227
L. Correia-Sá, S. Sousa, V. C. Fernandes, M. L. Maia,
C. Delerue-Matos, and V. F. Domingues
8 Remediation of Pesticide in Water . . . . . . . . . . . . . . . . . . . . . . . . . . 271
Muhammad Shahid Nazir, Zaman Tahir, Sadaf Ul Hassan,
Zulfiqar Ali, Majid Niaz Akhtar, Kashuf Azam,
and Mohd Azmuddin Abdullah

ix
x Contents

9 Strategy for the Inspection of Pesticide Residues in Food

and Agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
Sujoy Rano and Mukesh Singh
10 Toxic Effects of Pesticides on Avifauna Inhabiting Wetlands . . . . . 335
Sreedev Puthur, A. N. Anoopkumar, Sharrel Rebello,
Embalil Mathachan Aneesh, Raveendran Sindhu,
Parameswaran Binod, and Ashok Pandey
11 Analysis of Pesticide Residues in Biotic Matrices . . . . . . . . . . . . . . . 351
Barbara Clasen, Tamiris Rosso Storck, Eloisa Lovison Sasso,
and Tadeu Luis Tiecher

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
Contributors

Mohd Azmuddin Abdullah Institute of Marine Biotechnology, Universiti Malay-

sia Terengganu, Terengganu, Malaysia
Majid Niaz Akhtar Department of Physics, Muhammad Nawaz Sharif University
of Engineering and Technology (MNSUET), Multan, Pakistan
Zulfiqar Ali Department of Chemical Engineering, COMSATS University,
Islamabad, Pakistan
Embalil Mathachan Aneesh Communicable Disease Research Laboratory,
Department of Zoology, St. Joseph’s College, Irinjalakuda, India
A. N. Anoopkumar Communicable Disease Research Laboratory, Department of
Zoology, St. Joseph’s College, Irinjalakuda, India
Kashuf Azam Department of Chemistry, Postgraduate Islamia College, Lahore,
Pakistan
Parameswaran Binod Microbial Processes and Technology Division, CSIR-
National Institute for Interdisciplinary Science and Technology (CSIR-NIIST),
Trivandrum, India
María Verónica Cesio Departamento de Química del Litoral, Cenur Litoral Norte,
Universidad de la República (UdelaR), Paysandú, Uruguay
Cátedra de Farmacognosia y Productos Naturales, Departamento de Química
Orgánica Facultad de Química, Universidad de la República (UdelaR), Montevideo,
Uruguay
Barbara Clasen Environment and Sustainability Post Graduation Program, State
University of Rio Grande do Sul, São Francisco de Paula, RS, Brazil
Environmental Engineering Post Graduation Program, Federal University of Santa
Maria, Santa Maria, RS, Brazil

xi
xii Contributors

Marcos Colazzo Licenciatura en Análisis Alimentario, Instituto Tecnológico

Regional Suroeste, Universidad Tecnológica (UTEC), Polo Tecnológico Paysandú,
Paysandú, Uruguay
Luísa Correia Sá REQUIMTE/LAQV, Instituto Superior de Engenharia do Porto,
Instituto Politécnico do Porto, Porto, Portugal
Carlos Eduardo Carlos da Silva Soares Laboratory of Mycotoxicology and Food
Contaminants, Department of Food Science and Technology, Federal University of
Santa Catarina, Florianopolis, SC, Brazil
Fabiano Fabiano Dahlke Laboratory of Poultry Science, Department of Animal
Science, Federal University of Santa Catarina, Florianopolis, SC, Brazil
Cristina Delerue-Matos REQUIMTE/LAQV, Instituto Superior de Engenharia do
Porto, Instituto Politécnico do Porto, Porto, Portugal
Valentina F. Domingues REQUIMTE/LAQV, Instituto Superior de Engenharia
do Porto, Instituto Politécnico do Porto, Porto, Portugal
Virgínia Cruz Fernandes REQUIMTE/LAQV, Instituto Superior de Engenharia
do Porto, Instituto Politécnico do Porto, Porto, Portugal
Miguel Ángel González-Curbelo Departamento de Ciencias Básicas, Facultad de
Ingeniería, Universidad EAN, Bogotá D.C., Colombia
Javier González-Sálamo Departamento de Química, Unidad Departamental de
Química Analítica, Facultad de Ciencias, Universidad de La Laguna (ULL), San
Cristóbal de La Laguna, España
Instituto Universitario de Enfermedades Tropicales y Salud Pública de Canarias,
Universidad de La Laguna (ULL), San Cristóbal de La Laguna, España
Sadaf Ul Hassan Department of Chemistry, COMSATS University, Islamabad
Lahore campus (CUI), Lahore, Pakistan
Horacio Heinzen Departamento de Química del Litoral, Cenur Litoral Norte,
Universidad de la República (UdelaR), Paysandú, Uruguay
Cátedra de Farmacognosia y Productos Naturales, Departamento de Química
Orgánica Facultad de Química, Universidad de la República (UdelaR), Montevideo,
Uruguay
Javier Hernández-Borges Departamento de Química, Unidad Departamental de
Química Analítica, Facultad de Ciencias, Universidad de La Laguna (ULL), San
Cristóbal de La Laguna, España
Instituto Universitario de Enfermedades Tropicales y Salud Pública de Canarias,
Universidad de La Laguna (ULL), San Cristóbal de La Laguna, España
Helen Karasali Laboratory of Chemical Control of Pesticides, Department of
Pesticides Control and Phytopharmacy, Benaki Phytopathological Institute, Athens,
Greece
Contributors xiii

Ramen Kumar Kole Department of Agricultural Chemicals, Faculty of Agricul-

ture, Bidhan Chandra Krishi Viswavidyalaya, Mohanpur, West Bengal, India
M. Luz Maia REQUIMTE/LAQV, Instituto Superior de Engenharia do Porto,
Instituto Politécnico do Porto, Porto, Portugal
Rahul Mondal Food Safety Wing, Department of Health and Family Welfare,
Goverment of West Bengal, Swasthya Sathi, Kolkata, India
Muhammad Shahid Nazir Department of Chemistry, COMSATS University,
Islamabad Lahore campus (CUI), Lahore, Pakistan
Paula Paíga REQUIMTE/LAQV, Instituto Superior de Engenharia do Porto,
Instituto Politécnico do Porto, Porto, Portugal
Ashok Pandey Centre for Innovation and Translational Research, CSIR-Indian
Institute for Toxicology Research (CSIR-IITR), Lucknow, India
Lucía Pareja Departamento de Química del Litoral, Cenur Litoral Norte,
Universidad de la República (UdelaR), Paysandú, Uruguay
George Pavlidis Laboratory of Chemical Control of Pesticides, Department of
Pesticides Control and Phytopharmacy, Benaki Phytopathological Institute, Athens,
Greece
Andrés Pérez-Parada Departamento de Desarrollo Tecnológico – DDT, Centro
Universitario Regional del Este (CURE), Universidad de la República (UdelaR),
Rocha, Uruguay
Sreedev Puthur Communicable Disease Research Laboratory, Department of
Zoology, St. Joseph’s College, Irinjalakuda, India
Sujoy Rano Department of Biotechnology, Haldia Institute of Technology, Haldia,
Purba Medinipur, West Bengal, India
Sharrel Rebello Communicable Disease Research Laboratory, Department of
Zoology, St. Joseph’s College, Irinjalakuda, India
Eloisa Lovison Sasso Environment and Sustainability Post Graduation Program,
State University of Rio Grande do Sul, São Francisco de Paula, RS, Brazil
Vildes Maria Vildes Scussel Laboratory of Mycotoxicology and Food Contami-
nants, Department of Food Science and Technology, Federal University of Santa
Catarina, Florianopolis, SC, Brazil
Raveendran Sindhu Microbial Processes and Technology Division, CSIR-
National Institute for Interdisciplinary Science and Technology (CSIR-NIIST),
Trivandrum, India
Mukesh Singh Department of Biotechnology, Haldia Institute of Technology,
Haldia, Purba Medinipur, West Bengal, India
xiv Contributors

Sara Sousa REQUIMTE/LAQV, Instituto Superior de Engenharia do Porto,

Instituto Politécnico do Porto, Porto, Portugal
Tamiris Rosso Storck Environmental Engineering Post Graduation Program, Fed-
eral University of Santa Maria, Santa Maria, RS, Brazil
Zaman Tahir Department of Chemical Engineering, COMSATS University,
Islamabad, Lahore, Pakistan
Tadeu Luis Tiecher Federal Institute Rio Grande do Sul, Campus Restinga, Porto
Alegre, RS, Brazil
Diana Angélica Varela-Martínez Departamento de Ciencias Básicas, Facultad de
Ingeniería, Universidad EAN, Bogotá D.C., Colombia
Departamento de Química, Unidad Departamental de Química Analítica, Facultad
de Ciencias, Universidad de La Laguna (ULL), San Cristóbal de La Laguna, España
José L. Vera REQUIMTE/LAQV, Instituto Superior de Engenharia do Porto,
Instituto Politécnico do Porto, Porto, Portugal
About the Editors

Inamuddin is an Assistant Professor in the Department of Chemistry, King

Abdulaziz University, Jeddah, Saudi Arabia, and is also an Assistant Professor in
the Department of Applied Chemistry, Aligarh Muslim University, Aligarh, India.
He has extensive research experience in multidisciplinary fields of analytical chem-
istry, materials chemistry, electrochemistry, renewable energy and environmental
science. Dr. Inamuddin has published approximately 162 research articles in various
international scientific journals, 18 book chapters, and 96 edited books with multiple
well-known publishers. His current research interests include ion exchange mate-
rials, a sensor for heavy metal ions, biofuel cells, supercapacitors and bending
actuators.

Mohd Imran Ahamed received his Ph.D. degree on the topic “Synthesis and
characterization of inorganic-organic composite heavy metals selective cation-
exchangers and their analytical applications” from Aligarh Muslim University,
Aligarh, India, in 2019. He has published several research and review articles in
internationally acclaimed journals of. Dr. Ahamed has also edited various books
published by Springer, CRC Press Taylor & Francis Asia Pacific and Materials
Science Forum LLC, U.S.A. He has completed his B.Sc. (Hons) Chemistry at
Aligarh Muslim University, Aligarh, India, and M.Sc. (Organic Chemistry) at
Dr. Bhimrao Ambedkar University, Agra, India. His research work includes
ion-exchange chromatography, wastewater treatment and analysis, bending actuator,
and electrospinning.

Eric Lichtfouse is a Biogeochemist at Aix Marseille University who has invented

carbon-13 dating, a molecular-level method allowing to study the dynamics of
organic compounds in temporal pools of complex environmental media. He is
Chief Editor of the journal Environmental Chemistry Letters and the book series
Sustainable Agriculture Reviews and Environmental Chemistry for a Sustainable
World. Dr. Lichtfouse is the author of the book Scientific Writing for Impact Factor
Journals, which includes an innovative writing tool: the Micro-Article.

xv
Chapter 1
Determination of Pesticide Residues in Fish

Lucía Pareja , Horacio Heinzen , María Verónica Cesio ,

Marcos Colazzo , and Andrés Pérez-Parada

Abstract Pesticide residues occurring in fish of marine and freshwater media is a

continuous issue for food safety and environmental monitoring. In the last 40 years
the analysis of organohalogen pesticides in marine fish has been conducted seeking
to trace the bioaccumulation and biomagnification in food webs. The analysis of
organochlorine, highly lipophilic compounds, was performed using sample prepa-
ration methods with a large solvent consumption followed by instrumental determi-
nation using gas chromatography with electron capture detectors. Fish as an
analytical matrix presents particular challenges for residue analysis because of the
large amount of different edible species, the variable proportion of fatty tissues and
the they requirements for sample preservation. Moreover, different non-traditional
tissues such as gills or the brain are of recent interest in environmental monitoring
and pesticide exposure studies. In the last decades, new concepts for the sample
preparation of trace contaminants in fish have been developed, based on sample

L. Pareja (*)
Departamento de Química del Litoral, Cenur Litoral Norte, Universidad de la República
(UdelaR), Paysandú, Uruguay
e-mail: [email protected]
H. Heinzen · M. V. Cesio
Departamento de Química del Litoral, Cenur Litoral Norte, Universidad de la República
(UdelaR), Paysandú, Uruguay
Cátedra de Farmacognosia y Productos Naturales, Departamento de Química Orgánica Facultad
de Química, Universidad de la República (UdelaR), Montevideo, Uruguay
e-mail: [email protected]; [email protected]
M. Colazzo
Licenciatura en Análisis Alimentario, Instituto Tecnológico Regional Suroeste, Universidad
Tecnológica (UTEC), Polo Tecnológico Paysandú, Paysandú, Uruguay
e-mail: [email protected]
A. Pérez-Parada
Departamento de Desarrollo Tecnológico – DDT, Centro Universitario Regional del Este
(CURE), Universidad de la República (UdelaR), Rocha, Uruguay
e-mail: [email protected]

© The Editor(s) (if applicable) and The Author(s), under exclusive license to 1
Springer Nature Switzerland AG 2021
Inamuddin et al. (eds.), Sustainable Agriculture Reviews 47, Sustainable Agriculture
Reviews 47, https://doi.org/10.1007/978-3-030-54712-7_1
2 L. Pareja et al.

miniaturization and minimal reagent consumption capable of analyzing a large

palette of active principles, from non-polar to semi-polar ones.
The focus of this chapter is to present the complexity of the possible analytical
matrices and the different strategies used for pesticide residues determination. The
advent of liquid and gas chromatography coupled to tandem mass spectrometry,
expanded the scope of target compounds monitored in fish, particularly for fresh-
water agroecosystems. The application of new mass spectrometry techniques for
pesticide residue analysis in fish, along with the matrix effects observed with the
applied instrumentation are deeply discussed. The evidence about different pesti-
cides currently used worldwide and their occurrence in the tissues of freshwater fish
at trace levels is presented. The bioaccumulation of banned persistent organic
pollutants in edible fish is still a matter of interest for human exposure. Nevertheless,
the regulation of maximum residue limits of currently used pesticides seeking a safe
fish consumption is scarce.

Keywords Fish · Marine and freshwater · Currently used pesticides · Pesticide

residues · Sample preparation · Gas chromatography · Liquid chromatography ·
Hyphenated mass spectrometry · Environmental monitoring · Food safety

1.1 Introduction

Different fish species, from marine and freshwater habitats are a key source of food
for humans at global scale.
Synthetic organic contaminants have been monitored in edible fish from marine
origin for more than 40 years. However, the compounds, named as legacy contam-
inants or persistent organic pollutants still play a role on health risks to aquatic
ecosystems and human consumers (Boitsov et al. 2019; Pheiffer et al. 2018; Sun
et al. 2018; Wu et al. 2018). The monitoring of organochlorine pesticides in fish
muscle tissue initially started as a concern of bioaccumulation and biomagnification
research. Highly persistent and non-polar compounds with log octanol-water coef-
ficient higher than 5 such as hexachlorocyclohexane congeners, aldrin, and
dichlorodiphenyltrichloroethane were found to occur in fish muscle tissues particu-
larly associated to the high fat content (Pheiffer et al. 2018; Rios et al. 2019).
Widespread expansion of agricultural techniques based on application of pesti-
cides led to an increasing use and disposal of pesticide residues in aquatic environ-
ments worldwide. Chemical diversity of pesticides has changed over the last decades
and the currently used pesticides are, in general, more polar and less persistent.
Nevertheless, significant exposure is evidenced in agricultural basins for freshwater
fish species (Abalos et al. 2019; Ernst et al. 2018; Penland et al. 2018; Pheiffer et al.
2018; Picó et al. 2019; Vieira et al. 2019). The biological effect of the findings at
sublethal levels is not well understood. The presence of pesticide residues in fish as
multiple stressors in the aquatic environment can help to rationalize the effects of
contaminants on non-target aquatic biota (Vieira et al. 2019). A multidisciplinary
1 Determination of Pesticide Residues in Fish 3

approach would be helpful to integrate ecological, ecotoxicological and chemical

observations that will give, through pesticide residues in fish, a holistic vision of the
situation of a given environment.
Pesticide residues occurrence in fish is not only relevant from a toxicological
point of view. Fish exposed to different environments are useful sources of infor-
mation about the contamination level of the surrounding agroecosystems even at
basin scale (Ernst et al. 2018; Ríos et al. 2019; Vieira et al. 2019). Pesticides can be
incorporated onto fish tissues through the fish gills, either via water exposure or by
the ingestion of contaminated feed. The route by which the pesticide integrates the
fish body is relevant to assess contamination at muscle level. In the first case, no
biotransformation occurs; the pesticide could be incorporated as such. In the latter
case, the pesticide could be not only metabolized in the gastrointestinal tract but also
stored in the viscera, normally, the non-edible portion of fish. Other situations,
crucial to evaluate bioaccumulation or biomagnifications, are the habits of the
animals, either migratory or not, and the existing trophic interactions (Ernst et al.
2018; Pérez-Parada et al. 2018; Picó et al. 2019). From a physicochemical point of
view, when a compound shows a solubility in water lower than 0.0002 g/L, could be
adsorbed to the suspended organic matter in freshwater environments and distributed
within the fish tissues, no matter the route of exposure. Moreover, the amount of
lipids plays a significant role in the storage capability of fish species. Lipid amount
varies significantly seasonally, and has to be considered during pesticide residue
analysis (Crane et al. 2007; Pérez-Parada et al. 2018; Ríos et al. 2019; Wickham et al.
1997).
Exposure to different currently used pesticide families led to recent reports
showing pesticide occurrence ranging from pyrethroids and organophosphate insec-
ticides to fungicides. Bioaccumulation of strobilurins, triazoles, triazines and
chloroacetamide herbicides at μg/kg levels have been proved (Pérez-Parada et al.
2018). Additionally, some environmental organic contaminants like pharmaceuticals
and semi-polar pesticides with log octanol-water coefficient higher than 2, has been
detected in fish (Ernst et al. 2018; Picó et al. 2019; Rojo et al. 2019; Vieira et al.
2019). Considering the levels of pesticides residues found in fish it is important to
pay attention to the safety of fish consumption. Agricultural pesticides in fish are
assorted as extraneous chemicals. For that reason, extraneous maximum residue
levels (E-MRLs) is matter of current interest at Codex Alimentarius (Pérez-Parada
et al. 2018). Few pesticides are currently regulated and monitored in commercial
trade from those existing based on specific national requirements for both persistent
organic pollutants and currently used pesticides. Existing regulation deserves special
attention on a few specific substances handling maximum tolerance levels and action
levels (Food and Drug Administration 2011).
Summarizing, fish is one of the main aquatic organisms where an immediate
impact of contamination because of agricultural activities can be observed. Further-
more, is considered a fundamental component of a balanced diet. Since fish contri-
bution in nutrients is indisputable, is necessary to ensure the quality of fish to
preserve human health. For this reason, the evaluation of the level of pesticide
4 L. Pareja et al.

residues in fish is important to ensure food safety (Molina Ruiz et al. 2015;
Kalachova et al. 2013).
The interest in pesticide residues determination in seafood and particularly fish is
actually not new. Interestingly, some well-established sample preparation methods
for pesticide residues determination such as matrix solid phase dispersion were
developed for organochlorine pesticides determination in fish (Long et al. 1991).
New high throughput sample preparation methodologies, such as the variations of
QuEChERS coupled to new and highly sensitive and selective instrumental tech-
niques based on hyphenated mass spectrometry, has enabled a fast expansion of the
scope to multi-class organic contaminants in fish at trace levels (Barbieri et al. 2019;
Colazzo et al. 2019; Picó et al. 2019).
In this chapter, the determination of pesticides in fish, focused on contemporary
sample preparation approaches will be discussed. The advantages and disadvantages
as well as the coupling to modern tandem mass spectroscopic techniques will be
addressed. Moreover, potential features of recent analytical tools aiming lower
detectability of multi-class contaminants enabling an increase in knowledge of
pesticide dynamics in the aquatic environment and food safety will be shown.

1.2 Fish Matrix Considerations

Fish and fish body parts are considered complex and variable matrices. As fish does
not have a fixed chemical composition an approximate global composition, is
generally accepted (Table 1.1). Furthermore, other minor components such as
sugars, nucleotides and vitamins are also present. A thumb rule states that water
and fat are inversely correlated, adding 80% of fish composition.
From an environmental point of view, the presence of compounds with high n-
octanol-water partition coefficient such as persistent organic contaminants, pyre-
throids and strobilurins in liver and viscera of fish give relevant information.
Pesticide residues in the digestive apparatus of fish are indicative that the way of
entry, is through food and water consumption. Therefore, the contaminants can be
incorporated either from smaller fish, in a typical example of biomagnification or
from sediments, catch tissue, as well as suspended organic matter. A higher fre-
quency of dichlorodiphenyldichloroethylene findings in Cnesterodon
decemmaculatus, a sediment feeding fish, caught in lagoons surrounded by farms
where agricultural activities have been performed in the last hundred years was
reported (Pareja et al. 2013).

Table 1.1 General proximate Chemical composition Amount (%)

chemical composition of fish
Water 65–90
tissues
Protein 10–22
Fat 1–20
Mineral 0.5–5
1 Determination of Pesticide Residues in Fish 5

Fig. 1.1 Shows a typical fatty acid composition in fish fillet of Prochilodus lineatus captured in
Uruguay River. The chromatogram was obtained by gas chromatography mass spectrometry in full
scan mode. The main fatty acids are highlighted in blue; C14:0 myristic acid, C16:0 palmitic acid;
C-18:0 stearic acid, C-18:1 oleic acid, C-18:2 linoleic acid, C-18:3 linolenic acid

Pesticide findings in fish fillets are a relevant issue from the food safety point of
view. The possibility for the occurrence of residues in fish matrix is a combination of
physicochemical properties and body compartments that could allow the partition
between blood and tissues. Fat deposits are frequent in fish muscle, being the
depositories for the most lipophilic compounds. As described above, the character-
istics of the matrix varies not only with the fish species but also with the part of the
fish to be studied. Moreover, matrix composition changes dramatically within
species seasonally. The lipid amount increases when food is available but drops
down when fish are in the spawning season. In addition, different amounts and types
of lipophilic compounds such as vitamins, triglycerides, phospholipids, glycolipids,
sterols as well as long-chain polyunsaturated fatty acids, among others could be
present depending on the age and the fish species (Fig. 1.1). The composition of fish
matrix should be taken into account when designing the sample preparation and
instrumental determination technique because the described compounds can affect
the determination of the target residues in different ways.
The size of the animal is also of paramount importance. Little fish, smaller than
5 cm like Pomoxis spp, crappies, or Cnesterodon decemmaculatus, madrecitas, are
analyzed completes (Fig. 1.2). The aforementioned species are useful specimens for
caged experiments in water contamination research studies where the animal expo-
sure to the aquatic environment can be monitored in a given period of time. The
information gathered has relevance when evaluating the environmental status of a
given stream or catchments (Pareja et al. 2013).
In order to select a “fit for purpose” sample preparation method; the lipid content
in the tissues should be calculated before pesticide residues determination, (Choi
et al. 2016; Ernst et al. 2018; Molina Ruiz et al. 2015; Morrison et al. 2016; Yao et al.
2016). Different procedures are used for lipid determination: ISO 734-1:2008, Blight