Chapter 20c

Drug detectors
Sue M. Ford

20c.1
20c.1.1

DRUG DETECTION IN THE FIELD

Background considerations

Drug detection technologies are used in various law enforcement scenarios that present challenges for instrumentation development. Not only do the drugs which must be detected vary, but the amounts to be detected range from microgram quantities left as incidental contamination from drug activity to kilogram amounts being transported in hidden caches. The locations of hidden drugs create difculties in detection as well. Customs and border agents need drug detection technology to intercept drugs smuggled into the country in bulk cargo containers or carried by individuals. Correctional facility personnel search for drugs being smuggled into the prison by mail (e.g. small amounts under stamps) or by visitors, and furthermore need to monitor drug possession inside the prison. Law enforcement representatives may use detectors in schools to nd the caches of student dealers. Other customers for drug detection technology include aviation and marine carriers, postal and courier services, private industry, and the military. In all these cases, the problem is to reveal the relatively rare presence of drugs in a population of individuals or items, most of which will be negative. Consequently, for drug detection purposes the ability to nd illicit contraband is of greater importance than accurate quantitation.
20c.1.2 Desirable characteristics of eld detectors

Drug detectors are used on-site to screen items in transit, such as cargo, pieces of mail, or personal belongings of individuals. The units must be mobile or portable. Inasmuch as innumerable objects need to be scrutinized rapidly in order to minimize delays and inconvenience, the
Comprehensive Analytical Chemistry 47 S. Ahuja and N. Jespersen (Eds) Volume 47 ISSN: 0166-526X DOI: 10.1016/S0166-526X(06)47031-8 r 2006 Elsevier B.V. All rights reserved.

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process of screening should ideally be non-invasive, non-destructive, and rapid, and should display results within seconds. Instrumentation for drug detection in the eld must be simple enough to be used by trained non-scientic personnel and the output should be easily interpreted. Sample acquisition should be simple with little requirement of sample preparation. With the exception of the X-ray and CT scanners, which weigh 0.53 tons [1], instrumentation for drug detection in the eld is easily transported, and includes mobile desktop units as well as hand-held instruments. On-site drug detection necessitates all phases of analysis to be completed in the eld, including sample collection, processing for presentation to the analytical module, identication, and quantitation.
20c.1.3 Sampling

The ability to successfully discover trace amounts of contraband depends on the sampling methodology as well as the detector. Drug residue detection on individuals, luggage and personal effects, mail, currency, and other items such as newspaper may be assessed by particulate detection. The surfaces are swiped with a swab, pad, or paper disk (sample trap), or the particles are collected on a lter by moving a vacuum over the surface. For screening of multiple items, it may be sufcient to swipe several times at a time with individual analysis needed only if a positive result is obtained. The swab or trap may be extracted with solvent and the sample then introduced into the instrument. In some cases, samples collected on a TeonTM pad are heated in the instrument in order to volatilize the analyte. Most instruments operate either as vapor detectors or particle analyzers, although there are a few that can operate in both modes. Newer sampling devices, such as those employed by the US Transportation Security Administration (produced by Smiths Detection (London, England and Pine Brook, NJ) for explosives detection, blow puffs of air at passengers from head to foot. Particles which subsequently fall to the ground are collected by being sucked into vents for chemical analysis.
20c.1.4 Background contamination

Detection of drug residues that contaminate surfaces and vapors seeping from caches requires that the sensitivity of such methods is generally in the sub-microgram range. Individuals who have handled drugs may have residues on their hands in the range of 110 mg [2], which can
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remain at least 90 min after handling and handwashing [3]. Another application of trace detection is in screening currency, suspected of being used in illicit drug activity. Although the instrument should pick up the low quantities expected from handling in such situations, in some metropolitan areas most currency is contaminated with drugs and an instrument with the threshold set too low will generate many false positives.

20c.2
20c.2.1

INSTRUMENTATION
Bulk detection

Instrumentation for revealing the presence of bulk quantities of concealed drugs will differ from those developed to nd evidence of minute quantities on surfaces. Bulk detection is concerned with amounts ranging from grams to kilograms [4]. Bulk detection is done by manual inspection, X-ray, CT scans, and acoustic inspection. X-ray or CT scanners used as bulk detectors have sensitivity of 210 g, and suspect items are subsequently conrmed by chemical analysis. Hand-held acoustic inspection instruments such as the Acoustic Inspection Device (AID) and the Ultrasonic Pulse Echo (UPE) developed by Pacic Northwest National Laboratories/Battelle, can be used for analysis of cargo liquids in sealed containers of various sizes within seconds [5]. The acoustical velocity and attenuation of multiple echoes returned to the instrument is evaluated by software which compares the data to the shipping manifest.
20c.2.2 Trace detection

20c.2.2.1 Wipe and spray For evaluating a small number of samples, non-instrument-based kits are available which are rapid and do not require sample cleanup. Wipe and spray detection kits such as those from the Mistral Group (Bethesda, MD) can be purchased for single drugs, multiple drugs, and explosives. The surfaces to be tested are swiped with paper sample traps, which are then sprayed with a reagent which turns the color depending on the compound(s) present. The reagents have been modied to be stable in the kit, for example, a modied Fast Blue BB reagent for cannabinoids and a modied cobalt thiocyanate (Scott) reagent for cocaine. The sensitivity of these kits is in the 110 mg range.
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20c.2.2.2 Vapor detection Some contraband drugs have sufcient vapor pressure to be detected by vapor detectors (sniffers, electronic noses), which draw in air around the test area and introduce the sample directly into the instrument. With the ZNoseTM (Electronic Sensor Technology, LP, Newbury Park, CA), the components of the vapor are separated by a fast (10 s) gas chromatography system. The detector contains molecular recognition sensor arrays based on surface acoustic wave (SAW) technology. The individual sensors each contain a chemoselective polymer sorbent applied to the surface of acoustic wave transducers [6]. As each vapor component interacts with a particular polymer, the properties of the polymer change (mass, viscoelasticity, swelling), which in turn perturbs the velocity of the SAW. The resulting shift in resonance frequencies of multiple sensors contributes to the pattern of output. Electronic noses provide a distinctive visual output, similar to an inkblot, which can be used to identify complex vapors by the shape of the blot or print. Detection of vapors seeping from closed containers may be sufciently sensitive that opening the container may not be necessary. Vapor detectors work for drugs such as heroin and marijuana which have volatile components with sufcient vapor pressure for detection, whereas particle detection and swiping are more appropriate for other drugs. However, drugs without appreciable vapor pressure may be detectable in warmer temperatures or may have components that are distinctive enough to comprise an odor signature. For example, methyl benzoate is the component of street cocaine that dogs recognize and represents a signature molecule that can be detected with instrumentation. 20c.2.2.3 Biosensors Biosensors represent another technique for simple and rapid analyses in the eld (see Chapter 20a). Biosensors utilize proteins, including antibodies, enzymes, or receptors, which have afnities for specic chemicals. The proteins are incorporated into devices which produce a detectable response (e.g. color change) proportional to the amount of binding of analyte to the protein. Figure 20c.1 shows the general procedure for an enzyme-linked immunosorbant assay (ELISA). The proteins are chosen to bind specic compounds, such as the use of antibodies to detect cocaine or the enzyme acetylcholinesterase to detect organophosphate pesticides [7]. However, there is some degree of cross-reactivity. In some cases this may be advantageous in detecting structurally related derivatives such as metabolites [8]. Biosensors may
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Fig. 20c.1. ELISA assay. (a) Antibodies to the drug of interest are secured to a solid substratum such as a test tube or micro-well plate. The sample containing the analyte antigen is added to the reaction surface. (b) After the analyte has bound to the antibody, the vessel is rinsed to remove unbound antibody. A second antibody to the analyte is added. This antibody has a bound enzyme which has been chosen because its reaction produces a colored product which can be detected spectrophotometrically. (c) After this second antibody has bound to the rst antibodyantigen complex, the surface is again rinsed to remove unbound-antibody enzyme. The enzyme substrate is added in sufcient excess such that the rate of product formed is proportional to the amount of enzyme present. The enzyme-linked assays are very sensitive, since each enzyme can rapidly catalyze thousands of substrate to product reactions.

be incorporated into electronic equipment using piezoelectric transduction [7,9], in which case the binding event of antigen to antibody causes a change in the frequency of the signal from a piezoelectric transducer. A simpler, yet effective, use of immunoassay is illustrated by the single-use disposable devices such as the Drugwipes. The Drugwipes (Securetec Detektions-Systeme AG, Germany) is an immunoassay-based biosensor device that is available for opiates, cocaine, cannabis, and amphetamines. It can be used to assay surfaces as well
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as bodily uids such as sweat, saliva, and urine. Limited testing suggests that the low sensitivity of such biosensors in biological uids results in a high incidence of false negatives [10]. The method is about an order of magnitude more sensitive for surface detection [11]. The detection limits for cocaine are in the range of 34 ng/l (in water) for a piezoelectric immunosensor [7,9] to 50 ng/ml (in sweat, saliva) [11] for Drugwipes. 20c.2.2.4 Ion mobility spectrometry Ion mobility spectrometry (IMS) [3,12] is the most widely used instrument for drug detection. The sample is heated to vaporize the analyte, which is then ionized by atmospheric (ambient) pressure chemical ionization (APCI) [3]. The resulting gas-phase ions travel through a drift tube and are separated by their distinct velocities (mobilities) in a weak electrostatic eld. IMS instruments use ambient air or nitrogen as the carrier gas, making it particularly adaptable to eld applications. The ionization process for IMS is relatively mild, such that little or no fragmentation of the analyte occurs. A common ionization source for APCI is 63Ni, which is coated on a foil of gold or nickel [3]. The b-particle emitted reacts with nitrogen to produce a cascade of positive and negative ions, and secondary electrons. Collisions and subsequent reactions can result in proton transfer reactions and formation of clusters, dimers, and adducts. The drift gas for drug detection contains trace amounts of nicotinamide, which becomes protonated and can transfer the proton to the sample molecules [13]. 63Ni as an ionization source does limit the linear range and selectivity; however, it is advantageous for eld equipment because it does not require an external power supply, it is not prone to malfunction, and it has good specicity for its intended analytes. Other ionization methods, including photoionization, corona discharge, ame ionization, laser ionization, surface ionization, and electrospray ionization provide opportunities for extending the range and selectivity of IMS [3,14]. The linearity of IMS is not sufcient for accurate quantitation of analytes. However, detection of contraband essentially requires a positive/negative response, so that for this purpose linearity is not critical. The method is sensitive (sub-nanogram range) and has sufcient resolution ability [15,16]. The instrument can be adjusted to provide even better resolution for specic analytes of interest (e.g. drugs vs. explosives). These features, along with the reliability of the instrument, have made it the method of choice for eld operations. IMS instrumentation has undergone numerous modications that are promising for eld
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detection technology, including miniaturization to palm-sized units, redesign of drift tubes to increase resolution [1719], inclusion of a GC column or GS/MS as a pre-separator to reduce matrix effects [3,20], and improvements in sampling techniques [3,14]. Smiths Detection has recently introduced the Ionscan 500DT, which contains two IMS detectors and allows for simultaneous detection of narcotics and explosives in a single analysis. 20c.2.2.5 Mass spectrometry Mass spectrometry (MS) is a reliable laboratory method for identication and analysis of organic compounds (see Chapter 11). Successive generations of instruments have increased the power of analysis by interfacing MS with separation techniques such as gas chromatography. The advantages of MS methodologies over IMS include versatility in sample analysis, improved linearity, and accurate quantitation when necessary. The size of mass spectrometers has been reduced such that it is now feasible to transport the instruments for analysis in the eld [21,22]. Although the performance is generally inferior to laboratory-sited instruments, software can help minimize problems related to resolution. The limitations of MS compared to IMS are the bulk and complexity of instrumentation (e.g. vacuum, heating/cooling of GC column, power consumption) and more involved sample preparation. Additionally, the sampling and analysis times are longer, in the range of 15 min, compared to less than 20 s for IMS. MS technology is particularly valuable when specic identication of compounds is mandatory. The instrumentation size and the length of analysis preclude the use of MS for rapid screening of mail, luggage, and other high-throughput tasks. 20c.2.2.6 Raman spectroscopy Raman spectroscopy is used to identify substances based on the inelastic scattering of light. When light is applied to a molecule, the energy change between incident and scattered light depends on the structure of the molecule. Drugs and other complex molecules have many possibilities for interaction with light, and the spectrum of scattered light contains a characteristic pattern of peaks (ngerprint) that can be used to identify substances of interest [2]. The process is rapid, non-destructive, and requires minimal sample preparation [23]. The instruments can be congured with ber optic sample probes to detect chemicals on the ground and other surfaces. One application is to detect drugs in ngerprints while preserving the prints for other
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analyses [24,25]. It will also work through certain closed containers such as dark glass, plastic bags, and thin plastic containers. This, in particular, makes it more useful for eld applications than other spectroscopic methods such as FT-IR. A database of spectra is needed to determine whether compounds of interest are present or absent. FT-Raman spectra libraries are commercially available, including for illicit drugs [23]. Portable instruments suitable for eld use are available by InPhotonics (InPhototeTM), GE StreetLabTM (GE Ion Trak, Plainville, CT), RSL-1 Raman (Spectrolab, Berkshire, England), and RA series (Renishaw plc, Gloucestershire, UK). Software is available to dissect the spectra of interfering materials which may be mixed with the target substances.

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Drug detectors 11 R. McCullough, The use of the Drugwipe in a drug court setting. National Law Enforcement and Corrections Technology Center Rocky Mountain Regional Center, 5th Annual Innovative Technologies for Community Corrections Conference, Boston, MA, June 1416, 2004. T. Keller, A. Schneider, E. Tutsch-Bauer, J. Jaspers, R. Aderjan and G. Skopp, Ion mobility spectrometry for the detection of drugs in cases of forensic and criminalistic relevance, Int. J. Ion Mobility Spectrom., 2 (1999) 2234. T. Keller, A. Miki, P. Regenscheit, R. Dirnhofer, A. Schneider and H. Tsuchihashi, Detection of designer drugs in human hair by ion mobility spectrometry (IMS), Forensic Sci. Int., 94 (1998) 5563. F. Li, Z. Xie, H. Schmidt, S. Sielemann and J.I. Baumbach, Ion mobility spectrometer for online monitoring of trace compounds, Spectrochim. Acta-B, 57 (2002) 15631574. L.M. Matz and H.H. Hill Jr., Separation of benzodiazepines by electrospray ionization ion mobility spectrometry-mass spectroscopy, Anal. Chim. Acta, 457 (2002) 235245. J.A. McLean, B.T. Ruotolo, K.J. Gillig and D.H. Russell, Ion mobilitymass spectrometry: a new paradigm for proteomics, Int. J. Mass Spectrom., 240 (2005) 301315. I.A. Buryakov, Qualitative analysis of trace constituents by ion mobility increment spectrometer, Talanta, 61 (2003) 369375. I.A. Buryakov, Express analysis of explosives, chemical warfare agents and drugs with multicapillary column gas chromatography and ion mobility increment spectrometry, J. Chromatogr. B, 800 (2004) 7582. R.R. Kunz, W.F. Dinatale and P. Becotte-Haigh, Comparison of detection selectivity in ion mobility spectrometry: proton-attachment versus electron exchange ionization, Int. J. Mass Spectrom., 226 (2003) 379395. A.M. DeTulleo, P.B. Galat and M.E. Gay, Detecting heroin in the presence of cocaine using ion mobility spectrometry, Int. J. Ion Mobility Spectrom., 1 (2000) 3842. P.A. Smith, M.T. Sng, B.A. Eckenrode, S.Y. Leow, D. Koch, R.P. Erickson, C.R.J. Lepage and G.L. Hook, Towards smaller and faster gas chromatographymass spectrometry systems for eld chemical detection, J. Chromatogr. A, 1067 (2005) 285294. A.L. Makas and M.L. Troshkov, Field gas chromatographymass spectrometry for fast analysis, J. Chromatogr. B, 800 (2004) 5561. H. Tsuchihashi, M. Katagi, M. Nishikawa, M. Tatsuno, A. Nishioka, A. Nara, E. Nishio and C. Petty, Determination of methamphetamine and its related compounds using Fourier Transform Raman spectroscopy, Appl. Spectrosc., 51 (1997) 17961799. J.S. Day, H.G.M. Edwards, S.A. Dobrowski and A.M. Voice, The detection of drugs of abuse in ngerprints using Raman spectroscopy II:

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S.M. Ford cyanoacrylate-fumed ngerprints, Spectrochim. Acta Part A: Mol. Biomol. Spectrosc., 60 (2004) 17251730. J.S. Day, H.G.M. Edwards, S.A. Dobrowski and A.M. Voice, The detection of drugs of abuse in ngerprints using Raman spectroscopy I: latent ngerprints, Spectrochim. Acta Part A: Mol. Biomol. Spectros., 60 (2004) 563568.

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REVIEW QUESTIONS 1. 2. Describe some of the desirable characteristics of eld detectors. Describe briey operation of biosensors.

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