Analytical methods applied to the determination of pesticide residues in foods of animal origin. A review of the past two decades

doi:10.1016/j.chroma.2010.12.097

Journal of Chromatography A

Volume 1218, Issue 8, 25 February 2011, Pages 1021-1036

https://doi.org/10.1016/j.chroma.2010.12.097 Get rights and content

Abstract

Pesticides are widely used in agriculture and can be transferred to animals in a number of ways. Consequently, reliable analytical methods are required to determine pesticide residues in foods of animal origin. The present review covers published methods and research articles (1990–2010) in which pesticide residues have been extracted from meat and meat products, milk and dairy products, fish and seafood, and eggs, then cleaned up, and isolated by chromatographic techniques to be identified and quantified by various detection methods. Recovery rates, quantification limits, the matrix effect and related parameters have all been considered. Lastly, future developments in this field are outlined.

Introduction

Pest control in intensive agriculture involves treatment of crops (fruits, vegetables, cereals, etc.) pre- and post-harvests with a variety of synthetic chemicals generically known as pesticides [1]. Herbicides and insecticides are mainly used in the pre-harvest stages, rodenticides are employed in the post-harvest storage stages, and fungicides are applied at any stage of the process depending on the crop. These chemicals can be transferred from plants to animals via the food chain [2]. Furthermore, breeding animals and their accommodation can themselves be sprayed with pesticide solution to prevent pest infestations [3]. Consequently, both these contamination routes can lead to bioaccumulation of persistent pesticides in food products of animal origin such as meat, fish, fat, eggs, and milk.

Pollution by persistent chemicals is potentially harmful to the organisms at higher trophic levels in the food chain. Since diet is the main source of chronic exposure to low doses of these substances, humans are mainly exposed to these chemicals through ingestion [2], [4], [5]. The chronic effects of pesticides from food intake on human health are not well defined, but there is increasing evidence of carcinogenicity and genotoxicity, as well as disruption of hormonal functions [6], [7].

To ensure that pesticide residues are not found in food or feed at levels presenting an unacceptable risk for human consumption, maximum residue levels (MRLs) have therefore been set by the European Commission. MRLs are the upper legal concentration limits for pesticide residues in or on food or feed. They are set for a wide range of food commodities of plant and animal origin, and they usually apply to the product as placed on the market. MRLs are not simply set as toxicological threshold levels, they are derived after a comprehensive assessment of the properties of the active substance and the residue behaviour on treated crops.

Both the periodic estimation of human exposure to persistent organic pollutants and the establishment by the EU authorities of MRLs in foods have required the development of analytical methods suitable for research purposes and inspection programmes [7], [8], [9].

Most pesticide residue detection methods for food samples comprise two key preparation steps prior to identification/quantification: extraction of target analytes from the bulk of the matrix, and partitioning of the residues in an immiscible solvent and/or clean-up of analytes from matrix co-extractives, especially fat which interferes with assays [10], [11], [12], [13]. Complex samples such as meat products very often require a two-step clean-up which combines different chromatographic techniques in series [14]. When water-miscible extraction systems are used, such as with pesticide analysis in liquid milk for instance, it is also necessary to include a water removal or partitioning step [10].

However, most of these methods are time consuming and use large quantities of organic solvents to remove interference. Recent analytical developments have attempted to minimise the number of physical and chemical manipulations, the solvent volumes, the number of solvent evaporation steps, the use of toxic solvent, and have aimed to automate the extraction and clean-up procedures as far as possible [15].

Following the extraction/purification procedures, pesticide compounds are separated either on gas chromatography (GC) or liquid chromatography (LC), and then identified and quantified using different kinds of detection methods depending on the molecules to be analysed. Electron-capture detection (ECD), flame photometric detection (FPD), nitrogen–phosphorus detection (NPD), fluorescence detection, and diode-array detection (DAD) were mostly used for pesticide identification and quantification until recently. Many research papers on the analysis of pesticide residues in foods of animal origin report on the results achieved with these classical detection systems, even recently. But the expanding role of GC and LC coupled with mass spectrometry (MS) and tandem mass spectrometry (MS/MS) in pesticide residue analysis is clear in both monitoring and research applications.

The methodology for pesticide analysis in environmental and plant samples is very well documented and many examples are available in the literature. A number of recent reviews dealt with pesticide residue analysis in various foodstuffs [16], [17], [18], [19], [20], [21], [22], [23], [24]. However, none of these highlighted the problems, pitfalls and achievements in the foods of animal origin. Scientific documentation on analytical methods applied to pesticide determination in animal products is less abundant. This paper will aim to summarise the documentation published on the analysis of pesticide residues in meat and meat products, poultry and eggs, fish, and milk and dairy products over the past two decades.

Section snippets

Meat and meat products

Breeding animals can accumulate persistent organic pollutants from contaminated feed and water, and/or from pesticide application in animal production areas (treatment of cowsheds, pigsties, sheepfolds, warrens and/or treatment of animals themselves) [25]. While pesticide compounds are mostly stored in the fat and muscle of animals, they can also reach other compartments such as the brain, liver and lungs [26]. Consequently, these chemical residues have been studied in the meat [14], [27] and

Pesticides

In the reported studies from the literature consulted for this review, products of animal origin were mostly analysed for five main groups of pesticides, namely organochlorine pesticides, organophosphorus pesticides, carbamates, pyrethroids, and triazines. Few of them have been detected in various animal products (Table 1). However, various other pesticides have been studied during validation methods for detecting residues in foods of animal origin (Table 2).

Organochlorine pesticides (OCPs),

Extraction methods

In the past two decades, the most widely used pesticide extraction technique from foods of animal origin was direct solid–liquid extraction (SLE). This procedure consists in grinding chopped samples or extracted fats several times at high speed in selected organic solvents. This technical procedure has been applied to meat and meat products [3], [7], [11], [12], [15], [33], [35], [42], [43], [68], [69], [70], animal fat [14], [27], [29], [30], [36], offal [25], [29], [41], eggs [44], [45], [46]

Clean-up methods

Matrix constituents can be co-extracted and later co-eluted with analysed components and can consequently interfere with analyte identification and quantification. Moreover, co-extracted compounds, especially lipids, tend to adsorb in GC systems such as injection port and column, resulting in poor chromatographic performance [94]. A thorough clean-up minimises such matrix issues, improves sensitivity, permits more consistent and repeatable results, and extends the capillary column lifetime [1],

Separation and determination

At the present time, gas chromatography (GC) is the most widespread method for the separation and determination of most pesticides. However, liquid chromatography (LC) is also used for measuring levels of some pesticide residues such as carbamates and triazines, in foods of animal origin.

Recovery

In an analytical method, various extraction and clean-up steps are mixed and matched to achieve maximal analyte recovery with minimal matrix interference at the final measurement step [10]. Recovery has been defined by the IUPAC as “the proportion of the amount of analyte present in or added to the analytical portion of the test material which is extracted and presented for measurement” (IUPAC 1996 Symposium on harmonisation of quality assurance systems for analytical laboratories, Orlando, 4–5

Conclusion

The determination of pesticide residues in the environment and in foods is necessary for ensuring that human exposure to contaminants, especially by dietary intake, does not exceed acceptable levels for health. Consequently, robust analytical methods have to be validated for carrying out both research and monitoring programmes, and thus for defining limitations and supporting enforcement of regulations. In this field, reproducible analytical methods are required to allow the effective

Acknowledgement

The author would like to thank François Bordet (ANSES, Maisons-Alfort) for having read and for his pertinent advice on this manuscript, and Dary Inthavong and Frédéric Hommet (ANSES, Maisons-Alfort) for their support and for having answer to a few author's specific questions on the pesticide field. The author also thanks Jackie Godfrey (Coup de Puce, Toulouse) for her valuable assistance in the preparation of the English manuscript.

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ReviewAnalytical methods applied to the determination of pesticide residues in foods of animal origin. A review of the past two decades

Abstract

Introduction

Section snippets

Meat and meat products

Pesticides

Extraction methods

Clean-up methods

Separation and determination

Recovery

Conclusion

Acknowledgement

Environ. Pollut.

Environ. Pollut.

Sci. Total Environ.

Environ. Pollut.

Anal. Chim. Acta

J. Chromatogr. A

J. Chromatogr. A

Trends Anal. Chem.

Trends Anal. Chem.

Trends Anal. Chem.

Trends Anal. Chem.

J. Chromatogr. A

J. Chromatogr. A

Chemosphere

J. Chromatogr. A

Food Chem.

J. Chromatogr. A

Anal. Chim. Acta

J. Chromatogr. A

Chemosphere

Anal. Chim. Acta

Anal. Chim. Acta

J. Chromatogr. A

Environ. Int.

J. Hazard. Mater.

Chemosphere

J. Chromatogr. A

Talanta

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr. A

Ecotoxicol. Environ. Saf.

Chemosphere

J. Chromatogr.

J. Chromatogr. A

Chemosphere

J. Chromatogr. A

J. Chromatogr. A

J. Chromatogr.

Pestic. Sci.

J. Environ. Sci. Health B

Environ. Res.

Analysis

JAOAC

JAOAC

JAOAC

Anal. Bioanal. Chem.

J. Agric. Food Chem.

Mass Spectrom. Rev.

Review
Analytical methods applied to the determination of pesticide residues in foods of animal origin. A review of the past two decades