Rapid screening procedure based on headspace solid-phase microextraction and gas chromatography–mass spectrometry for the detection of many recreational drugs in hair

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Abstract

An increasing number of synthetic drugs are appearing on the illicit market and on the scene of drug use by youngsters. Official figures are underestimated. In addition, immunochemical tests are blind to many of these drugs and appropriate analytical procedures for routine clinical and epidemiological purposes are lacking. Therefore, the perceived increasing abuse of recreational drugs has not been proved yet. In a previous paper, we proposed a procedure for the preliminary screening of several recreational substances in hair and other biological matrices. Unfortunately, this procedure cannot apply to cocaine. Consequently, we performed a new headspace solid-phase microextraction and gas chromatography–mass spectrometry (HS-SPME–GC–MS) procedure for the simultaneous detection of cocaine, amphetamine (A), methamphetamine (MA), methylen-dioxyamphetamine (MDA), methylen-dioxymethamphetamine (MDMA), methylen-dioxyethamphetamine (MDE), N-methyl-1-(1,3-benzodioxol-5-yl)-2-butanamine (MBDB), ketamine, and methadone in human hair. Hair was washed with water and acetone in an ultrasonic bath. A short acid extraction with 1 M hydrochloric acid was needed; the fiber was exposed to a 5 min absorption at 90 °C and thermal desorption was performed at 250 °C for 3 min. The procedure was simple, rapid, required small quantities of sample and no derivatization. Good linearity was obtained over the 0.1–20.0 ng/mg range for the target compounds. Sensitivity was good enough: limits of detection (LOD) were 0.7 ng/mg of hair for the majority of substances. The intra-day precision ranged between 7 and 20%. This paper deals with the analytical performance of this procedure and its preliminary application to hair samples obtained on a voluntary basis from 183 young people (138 males and 45 females) in the Rome area.

Introduction

The abuse of amphetamine-like drugs and other stimulants is one of the most serious problems among Italian youths attending recreational settings [1], [2], [3], [4]. In Italy, like in other European countries, data on the spread of illicit drugs, especially synthetic ones, strongly depend on law enforcement seizures, on information from public facilities for treatment of drug addicts, and on self-reported studies. All these sources provide underestimated figures: very few analytical data are produced on substances available on the street market, and very few people abusing recreational drugs refer to public facilities intended for treatment of addicts [5]. Self-reported information suffers from credibility as it relies on the subjective memory for both long-term and recent use. In fact, some studies show that urine tests values and self-reports are poorly correlated [6], [7]. The analysis of seized “ecstasy” tablets performed by different laboratories in Italy in 1998 and 1999 revealed quali-quantitatively significant fluctuations in the content of substances per tablet [8]. A number of tablets (approximately 30%) do not contain MDMA, but other substances or active ingredients. The term “ecstasy” has become generic for a wide range of compounds as EMCDDA (European Monitoring Centre for Drugs and Drug Addiction) has claimed since 1997. Since the composition of tablets sold as “ecstasy” varies considerably, unknown types and quantities of drugs are taken by “ecstasy” users.

At present, the Italian legislation on drugs allows testing only of seized pills. Therefore, contrary to what happens in other countries [9], [10], the composition of products currently available on the street market in Italy cannot be assessed.

At present, considerable delay is foreseen in the adoption of a suitable procedure that relies on a compatible legal framework. In view of such difficulties and the growing concerns about the dangers of using these substances, a different analytical approach is advisable in order to evaluate the illicit use of drugs in a defined population such as young people at recreational venues. Unfortunately, the epidemiology of the use of synthetic drugs is hampered by the lack of analytical methodology. In particular, screening procedures for most recreational drugs are still unavailable. Headspace solid-phase microextraction (HS-SPME) coupled with a GC–MS applied to hair has recently been suggested [11]. Hair analysis has recently proved to be a useful technique for long-term control of the intake of many abused substances [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [26]. HS-SPME–GC–MS has had an increasing role in hair testing; several studies on the usefulness of this procedure for analysis of drugs in this biological matrix have been published [27], [28], [29], [30], [31], [32]. In a previous paper [11], we reported a simple, HS-SPME–GC–MS, one step procedure suitable for the simultaneous determination of many recreational drugs. This procedure, however, was unable to detect cocaine. The two ester groups of cocaine were easily hydrolysed in 30% sodium hydroxide [30], which could result in a restricted applicability of the procedure in recreational settings. In fact, cocaine is unfortunately becoming increasingly popular among young people in Italy as well as in other countries [5], [33]. This substance is now appearing in “ecstasy” tablets and can lead to the increasing abuse of polysubstances. Based on these observations, a screening procedure for the simultaneous detection of cocaine and amphetamine-like drugs has become a critical need. On these grounds, we set up a new HS-SPME–GC–MS procedure which requires an acid extraction, but no additional sample treatment or derivatization, and by which the main recreational drugs can be detected and quantified.

The present paper describes this simple and rapid procedure that can be used for screening purposes. Furthermore, we report the results of a preliminary application to the analysis of 183 hair samples obtained from young people in recreational settings.

Section snippets

Chemicals

Amphetamine (A), methamphetamine (MA), methylen-dioxyamphetamine (MDA), methylen-dioxymethamphetamine (MDMA), methylen-dioxyethamphetamine (MDE), N-methyl-1-(1,3-benzodioxol-5-yl)-2-butanamine (MBDB), ketamine, methadone and cocaine hydrochloride standards (1 mg/ml in methanol) were purchased from Sigma-Aldrich (Milan, Italy); 3,4 methylen-dioxypropylamphetamine (MDPA) hydrochloride standard (1 mg/ml in methanol) was purchased from SALARS (Como, Italy). Ketamine (Ketavet 50) was obtained from

Results and discussion

Major issues, such as analysis procedure, type of fiber used, extraction method, treatment of the matrix, adsorption and desorption conditions, were addressed by meeting most of the criteria reported in the literature on the development of HS-SPME methods [15]. However, for the detection of cocaine in the compounds mixture a compromise had to be reached.

Acknowledgements

We gratefully acknowledge the Social Agencies “PARSEC”, “IL CAMMINO”, “LA TENDA”, “MAGLIANA 80”, for specimen collection.

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