Methodology for the Identification of 117 Pesticides Commonly Involved in the Poisoning of Wildlife Using GC-MS-MS and LC-MS-MS

Abstract

Poisoning with agricultural chemicals is a major threat for wildlife all over the world. We have developed and validated an analytical scheme aimed to the identification and quantification of a wide range of pesticides in fresh liver from wildlife specimens that are routinely delivered to the forensic laboratories for toxicological investigation. The proposed method is comprised of a general solid-liquid extraction followed by purification steps and three complementary liquid or gas chromatographic analyses with triple quadrupole mass spectrometry detection. The developed methodology allows for the determination of 117 highly toxic pesticides in a variety of samples from wildlife poisoning incidents. The validity of the method has been demonstrated in samples from 98 real cases submitted to our laboratory between 2010 and 2012. This method allowed the identification and quantification of poison in 78 of 94 fresh liver samples from wild animals and was successfully used for the identification of pesticides in 35 of 46 non-liver samples. Therefore, the extraction and cleanup method with minor modifications and the potency of triple quadrupole mass spectrometry allow this method to be used to simultaneously detect and quantify or semi-quantify a majority of the most toxic pesticides in a variety of complex and degraded matrices.

A molecularly imprinted nanofilm‐based quartz crystal microbalance sensor for the real‐time detection of pirimicarb

“…In past years, pesticide residues in food were detected by different chromatographic methods . Although chromatographic methods possess the key advantages of accuracy and sensitivity, their disadvantages include high cost, difficulty of use, complex and higher‐quantity sample pretreatment, inability to perform online analysis, and the use of large amounts of organic solvents .…”

Intentional Carbofuran Poisoning in 7 dogs

“…The investigation of an incident that involves the death of wildlife specimens generally consists of a field inquiry, a postmortem examination and when necessary, chemical analysis to determine whether a poison might be responsible (5). For pesticide detection, multistage mass spectrometry (MS/MS) is considered a very useful tool to detect low levels of an analyte when coupled with chromatographic techniques (22). For our toxicological analysis, we used a triple quadrupole mass spectrometry analyzer, operated in the selective reaction monitoring mode which improved significantly both the sensitivity and selectivity of the analytical determination, as the Luzardo et al In our study, the pathological exam revealed predominant pulmonary lesions.…”

“…As a similarity the use of sonication should be mentioned, which improves the extraction efficiency and improve the recoveries of certain key pesticides, such as carbofuran. Therefore Luzardo et al(22) added a 5-min sonication to the extraction protocol, which in our cases lasted 15-min. Another method using homogenized 2 g liver samples is based on a new analytical multiclass method named QuEChERS technique(35), developed by Sell et al and validated according to the requirements of SANCO/12571/2013(34).…”

Humans Are Animals, Too: Critical Commonalities and Differences Between Human and Wildlife Forensic Genetics

“…The modern field of forensic sciences dates back to the 1800s and includes analysis of latent fingerprints, questioned documents, hair morphology, serology, and ballistics. Some wildlife forensic applications use these same classic techniques: fingerprints lifted from traps, feathers, eggs, or elephant tusks , microscopic examination of bullets retrieved from a carcass , or toxicological analysis of remains for the presence of poisons . Though the evidence items and the species involved differ between wildlife and human forensic laboratories, the point of many of these classic analyses is the same—to determine who was involved and how and where the crime occurred.…”