Comparative analysis of heroin and cocaine seizures

Journal of Chromatography B, 733 (1999) 127–136www.elsevier.com/ locate /chromb

Review

Comparative analysis of heroin and cocaine seizures

*M. Chiarotti , N. FucciIstituto di Medicina Legale Universita’ Cattolica S. Cuore, L.go F. Vito n.1, 00168 Rome, Italy

Abstract

In this brief review the analytical techniques mainly used for comparative analysis of both cocaine and heroin seizures arereported. The characterization of illicit samples is carried out by means of a variety of techniques including thin-layerchromatography, high-performance liquid chromatography, gas chromatography and capillary electrophoresis. By means ofthese technique it is possible to resolve some component in illicit drugs and their application for comparative analyses isdescribed in this review. Owing to the complexity and the variability of the mixture related to the origin and manufacturingimpurities a unique analytical approach based on the application of a single technique it is not sufficient to achieve therequested global characterization of the sample for comparative purposes. Generally a complete characterization is obtainedfocusing on the identification of minor and major components, origin and manufacturing impurities other than tracecompounds such as solvent residues. Nevertheless the application of a single robust methods able to resolve any possiblesignificant marker compounds, is still not described and there is a need for a standardized general procedure suitable for acomplete cross-examination of analytical data related to comparative analyses that can be carried out at an internationallevel. 1999 Elsevier Science B.V. All rights reserved.

Keywords: Reviews; Heroin; Cocaine

Contents

1. Introduction ............................................................................................................................................................................ 1282. Heroin .................................................................................................................................................................................... 128

2.1. Background .................................................................................................................................................................... 1282.2. Analytic methods ............................................................................................................................................................ 129

2.2.1. Thin-layer chromatography (TLC) and high-performance thin-layer chromatography (HPTLC)................................ 1292.2.2. High-performance liquid chromatography (HPLC) ................................................................................................ 1302.2.3. Gas chromatography and high-resolution gas chromatography (HRGC) .................................................................. 1302.2.4. Capillary electrophoresis (CE) ............................................................................................................................. 1302.2.5. Gas chromatography combustion isotope ratio mass spectrometry (GCC–IRMS)..................................................... 1312.2.6. Atomic absorption spectroscopy (AAS) ................................................................................................................ 131

3. Cocaine .................................................................................................................................................................................. 1313.1. Background .................................................................................................................................................................... 1313.2. Analytical methods ......................................................................................................................................................... 132

3.2.1. Thin-layer chromatography and high-performance thin-layer chromatography ......................................................... 1323.2.2. Gas chromatography and GC–MS ........................................................................................................................ 1323.2.3. High-performance liquid chromatography ............................................................................................................. 133

*Corresponding author.

0378-4347/99/$ – see front matter 1999 Elsevier Science B.V. All rights reserved.PI I : S0378-4347( 99 )00240-6

128 M. Chiarotti, N. Fucci / J. Chromatogr. B 733 (1999) 127 –136

3.2.4. Capillary electrophoresis...................................................................................................................................... 1333.3. New coca leaves alkaloids ............................................................................................................................................... 134

4. Conclusions ............................................................................................................................................................................ 134References .................................................................................................................................................................................. 135

1. Introduction The study of these impurities or of the possibledegradation products is very useful to trace back to a

The international concern about drug abuse re- specific illegal production process and for the com-quires precise and reliable data on the epidemiology parative analysis of two or more separate drugof this phenomenon, which should be apt to be used samples. Furthermore, the so-called origin im-for both preventive and repressive purposes. Further- purities, i.e., the natural substances that can be foundmore, the relevance of international traffic of illicit originally in the raw material and that can still bedrugs demands updated knowledge of the routes and found in traces in the final product in spite of thethe distribution network. procedures of extraction, purification and of possible

To this aim, important information is provided by transformation of the initial product, are likewisechemical–toxicological analysis of the samples of useful for comparative purposes.confiscated substances. Furthermore, the internation- The characterization of all these minor compoundsal character of the cocaine and heroin abuse phenom- in the drug samples confiscated on different occa-enon highlights the need that the results obtained can sions and/or in different places provide uniquebe compared at an international level. For this pieces of evidence in order to prove a commonreason, it is important that illicit drug preparations origin. This may allow one to reconstruct the routesundergo standardized chemical analyses in order to of the illegal traffic of the narcotic.achieve the best reliability and inter-laboratory com-parability.

Nevertheless, it is necessary to keep in mind that 2. Herointhe complete characterization of a drug samplecoming from an illegal market, done for a compara- 2.1. Backgroundtive purpose, may need various analytical steps andmethodological approaches, sometimes very differ- All the heroin samples confiscated in the illegalent. In reality these procedures are often difficult to market come directly or indirectly from opium, astandardize. substance extracted from the plant Papaver som-

However, it is sure that a detailed chemical niferum. In fact morphine derives from this plant andcharacterization of a natural or synthetic narcotic is heroin is produced from morphine by acetylation ofcrucial for the success of the many control activities the hydroxyls in the C-3 and C-6 positions.of the illicit drug trading [1–4]. Besides, in illicit The Papaver somniferum is part of the poppydrug analysis the identification of minor components, family (Papaveraceae), herbaceous plants with alter-such as, for example, the impurity due to the origin nate leaves; the poppy is probably a native plantor to the synthesis, is of crucial importance. from the Middle East. It is an annual plant with

During the preparation of an illicit drug, both of many known subspecies since the plant is able tonatural origin such as cocaine or of a semisynthetic hybridize, changing its characters, and these can varyorigin such as heroin, all the procedures of ex- according to the environmental factors. Under thesetraction, purification, synthesis (or semisynthesis) conditions it is difficult to make a classification, butinvolve the use of different chemical products (acids, it seems certain that of all the poppy family only P.bases, solvents, catalysts, etc.). These may leave somniferum and P. setigerum contain morphine [5].traces in the final product or may produce specific Opium contains various alkaloids, the most impor-alterations in the chemical structure of some of the tant of which are morphine and papaverine.components of the drug. The preparation of heroin requires the separation

M. Chiarotti, N. Fucci / J. Chromatogr. B 733 (1999) 127 –136 129

of morphine from opium [6]. This separation is origin impurities, heroin samples may be roughlyalmost never completely efficient because in the final divided in three principal types of different geog-product not negligible quantities of codeine, raphic origin: heroin from south-west Asia, heroinpapaverine, noscapine and meconine can still be from south-east Asia and Middle East heroin. Thesefound. Acetic anhydride is used for the acetylation, different type of heroin are characterized by differentsometimes together with organic bases, at varying amounts of opium alkaloids and related compoundstemperatures and times. During the process of (i.e., noscapine, papaverine and acetyltebaol) [6–9].acetylation a first intermediate product of the syn- In recent years, initially, the amount of morphine

3thesis, 0 -monoacetyl morphine, is formed. Then and of acetyl derivatives has been considered withheroin is formed, and finally it is in part sponta- respect to codeine and acetylcodeine, then the quan-

6 3neously deacetylated into 0 -monoacetyl morphine. titative ratios between 0 -monoacetyl morphine and6During this process, if other alkaloids, that can be 0 -monoacetyl morphine has been considered indica-

found as impurities in the original morphine, have tive for the modality of the acetylation processfunctional groups which can react with acetyl radi- [10,11]. Recently, the identification of tebaine by-cals, they will produce acetyl derivatives, such as in products (tebaol, acetyltebaol and phenantrenic de-the case of codeine. If they do not react with acetyl rivatives), that result in different amounts during thegroups, they will remain unchanged in the final acetylation process, depending on the temperatureproduct such as for papaverine and noscapine. and the duration of the process have been pointed out

If, on the other hand, they are chemically unstable, as useful for comparative purposes [12–15].as in the case of tebaine, they will form a variety of Besides the presence of meconine [16] and otherrearrangement and acetylation by-products. minor opium alkaloids (such as norlaudanosine) [17]

Heroin purification is generally done by separation as well as the characterization of the residues ofof the free base in alkaline medium, then crys- volatile substances [18] or of the trace of metals [19]tallization as hydrochloride salt after active charcoal has been also proposed for a complete chemicaltreatment. This general procedure is subjected to analysis of the samples.many variations including preliminary purification of Results of in depth chemical analysis performedthe morphine, that sometimes is completely omitted on various samples of heroin, of known geographiceffecting a process of acetylation of rough opium, area of production [9,20,21] has been referred, thesethe different procedures of refining heroin and the studies, pointed out the qualitative and quantitativeclassic steps of adulteration and dilution carried out variations that may take place in samples of heroinduring the illegal traffic. stored in different ways and for different times, are

In short the chemical composition of heroin particularly useful to evaluate the importance of eachavailable in the clandestine market depends on many single compound used in comparative analysis.factors, as summarized in Scheme 1. Each one ofthese theoretically can give way to the presence of 2.2. Analytic methodsspecific minor compounds on which the comparativechemical analysis is focused. 2.2.1. Thin-layer chromatography (TLC) and high-

On the basis of the presence of specific adulterants performance thin-layer chromatography (HPTLC)and diluents, in addition to some of the principal An initial screening of the heroin samples may be

easily done with TLC [22,23], which has the charac-teristics of being easy, economic and rapid. ThisOpium compositionanalytical method is not only useful to determine theMethods used for the extraction of morphine

Morphine acetylation procedures primary alkaloids of opium but also for the identifi-Purification of the mixture through the addition of different cation of other minor compounds deriving from thesolvents acetylation process of morphine [13,14].Base heroin precipitation and its purification

These techniques were already reported for com-Conversion from base heroin to its hydrochloride saltsparative purposes in 1970 when Curry and Patterson

Scheme 1. Factors affecting the final composition of illicit heroin. [24] used infrared spectroscopy, TLC and gas–liquid


chromatography to obtain qualitative information qualitative profile of the impurities from synthesisconcerning the presence of heroin as well as other process. In fact, it has been shown that even whenopium alkaloids in street powder and the determi- two samples have the same qualitative profile fornation of adulterating substances. minor components, they can derive from different

synthesis or semi-synthesis procedures.2.2.2. High-performance liquid chromatography These data confirm the necessity of applying(HPLC) different methodological approaches in order to

HPLC [25–29] is applied with great advantages perform an efficient comparative study of separatewith ultraviolet [8,30] or fluorescence detection specimens.[31,32]. In the latter case, the high selectivity of the The characterization of the residual solvents asdetector allows one to characterize the illegal sam- well as any volatile compound used during the illicitples on the basis of the presence of specific fluores- manufacturing can be considered a valid aid incent substances, linked mainly to the degradation comparative analysis. The identification of theseproducts of tebaine. solvents has been achieved through head space GC,

Ultraviolet and fluorescence detection can also be carried out directly on the clandestine preparations ofused in tandem [12,35]. Also, electrochemical de- the drugs [18].tection has been proposed in order to enhance the Barnfield et al. [47] suggested, for routine pur-sensitivity [33–35,38]. poses, gas chromatographic analysis without sample

HPLC offers the possibility of direct identification pre-treatment for the identification of both the princi-of sugar and other carbohydrates (diluents) [36,37] pal components and minor compounds. It was beenwithout derivatization reactions, as is required for already stressed [48] the importance in comparativegas chromatography (GC). Avoiding any derivatiza- analysis of the quantitative evaluation of morphinetion steps renders the analytical procedure more and codeine content and their relative ratios. Thereproducible when the results are to be compared quantitative evaluation was applied also to thefrom data produced by different laboratories. relative content of their products of acetylation

(heroin and acetylcodeine). According to these au-2.2.3. Gas chromatography and high-resolution thors, the correlation between the principal opiumgas chromatography (HRGC) alkaloids was rather constant in the samples coming

Many of the suggested methods for the chemical from the same illicit batch, and it did not changecharacterization of heroin samples are based on the significantly following adulteration and dilution pro-use of gas chromatographic techniques, at the begin- cesses.ning with packed columns [4,10,31,39–41] usually Eventually, GC coupled with mass spectrometrycoupled with flame ionization detection (FID) or (MS) has undoubtedly brought advantages in termselectron-capture detection (ECD) [10,42,43,49], later of specificity and sensitivity; GC–MS as been main-with capillary columns [17,21,42,44,57]. ly used to identify substances in trace amounts

With the use of gas chromatographic techniques, previously not identified by GC–FID. According toproblems related to the decomposition and rearrange- the modern literature, GC–MS has to be consideredment phenomena during the analytical process, have a useful tool for comparative purposes [7,8,50,51].been reported [45,46] by different authors. It must bepointed out that the organic compounds found intraces in heroin samples are mainly constituted by 2.2.4. Capillary electrophoresis (CE)degradation products of opium alkaloids produced In the last part of this decade CE has foundduring the acetylation step [17], so it is crucial to be application for the separation of the acid and neutralable to accurately discriminate the compounds really impurities in heroin [52,53]. CE has been used withcontained in the sample from the possible artefacts UV or laser-induced fluorescence (LIF) detection,produced during the gas chromatographic analysis. which remarkably increases the sensitivity [52].In this regard Neumann [46] pointed out that it is not This method has shown to be suitable both forwise to limit the comparative study exclusively to the heroin samples and for rough opium, however a


careful preparation of the sample before the in- coca, through a process of extraction with organicstrumental analysis is generally required [54]. solvents followed by various procedures of purifica-

tion including treatment with potassium permanga-2.2.5. Gas chromatography combustion isotope nate, liquid–liquid extraction and a final conversionratio mass spectrometry (GCC–IRMS) from free base cocaine to hydrochloride cocaine

Recently, the study of the relative ratios of the [58].natural isotopes of carbon and nitrogen has been There are four recognized varieties [59–63] ofproposed as a promising method for the determi- coca plants deriving from two species that containnation of the geographic origin of illicit drugs, and significant levels of cocaine; they are: Eritroxylonfor the comparative analysis. The evaluation of the coca var. coca (ECVC); E. coca var. ipadu (ECVI);

12 13relative ratio C/ C may be carried out both E. coca var. novogranatense (ECVN); E. novo-directly on the heroin and after hydrolysis. granatense var. truxillense (ENVT). Historically,

Thus it is possible to carry out a comparative ECVC is the one most used for the preparation ofanalysis both on the original product (morphine) and street cocaine.on the end product of the processing (heroin) Due to the coarse clandestine processing, many[55,56]. impurities can be present in the final products

In fact, the relative amount of the carbon and introduced into the illegal market.nitrogen isotopes in a plant and in the product The origin impurities are minor compounds thatderived from it are characterized by the photo- can be found in coca leaves (cis and trans cin-synthesis cycle and by the metabolic cycle of carbon, namoylcocaine, tropococaine, hydroxycocaine, tri-nitrogen, oxygen and hydrogen uptake [56]. metoxycocaine, truxillines). Other impurities are

Furthermore, environmental conditions such as related to by-products resulting during the clandes-humidity, temperature and isotopic composition of tine process.environmental carbon dioxide in which the plant has Among the origin impurities, cis and trans cin-grown may influence the isotopic content. namoylcocaines are widely studied for comparative

These concepts applied to comparative analysis of purposes, because of their stability and their easydrugs show that this analytical procedure is able to identification, possible with different techniques [64–provide data not affected by storage, dilution or 66].adulteration. The truxillines are natural alkaloids that can be

found in the coca leaves and their content varies2.2.6. Atomic absorption spectroscopy (AAS) significantly from one sample to another [67]. The

The analysis of traces metals in the comparative variation in truxilline amount depends on the tax-field has been proposed rarely, mainly because of onomic variety of the plant used or by differentproblems related to the evaluation of the results. clandestine working procedure.Particularly, it has not been possible so far to find The identification of these substances in streetout one or more elements that can be considered as cocaine samples is quite recent [67,68], even if thediscriminative for comparative tests. presence of a- and b-truxillines in coca leaves has

The method is essentially based on the miner- been described by Moore et al. [67] who, for the firstalization of the sample by nitric acid followed by time, reported their nine isomers.AAS [19]. The truxillines are quite stable and are not affected

by illicit chemical treatment of the drugs. So thesecompounds are considered suitable tools for com-

3. Cocaine parative analysis; on the other hand their completeidentification is not easy and requires sophisticated

3.1. Background analytical procedures.The presence of tropococaine in street cocaine

Whole cocaine which is available in the clandes- samples seems to be very variable, probably linkedtine market comes from the leaves of Eritroxylon to the plant’s taxonomy. In fact, its content seems to


be lower in the ECVC type of plant with respect to (A) Origin impuritiesthe ENVN and ENVT types [69–71]. The com- Cinnamolycocaines, tropococaine, truxilline, hydroxycocaines,

trimethoxy analogues of cocaine, cuscohygrine, hygrineputerized analysis of relative ratios betweentropococaine, norcocaine, cinnamoilcocaines and

(B) Manufacturing by-productscocaine has been reported [69].Oxidation products

Benzoylecgonine, ecgonine, ecgonine methylester N-Norcocaine, N-acetylnorcocaine, N-formylnorcocaine,and benzoic acid, [72–74] are the principal hy- N-benzylnorecgonine methyl ester, N-norecgonine methyl esterdrolysis by-products of cocaine. These compounds Hydrolyis productsmainly originate during the purification of the drugs, Benzoylecgonine, ecgonine, ecgonine methylester, benzoic acid,but they can be also produced by inadequate cocaine cinnammic acids, truxininc and truxillic acids

storage. Cinnammic acids, truxinic acids and truxillic Solvent residuesacids, are other hydrolysis by-products proposed as Dimethyl ketone, diethyl ether, methyl ethyl ketone, etc.useful for comparative purposes [75–79].

Scheme 2. Origin impurities and manufacturing by-products ofThe N-nor series (N-formylnorcocaine, N-nor-cocaine.cocaine, N-benzoylnorecgonine methylester, N-

norecgonine and N-acetylnorcocaine) impurities aredue to the use of oxidants during the clandestine For example in a recent work [78], the separation ofproduction [80–85]. origin impurities by TLC is described in samples of

The presence of process by-products can be seized cocaine.related also to the pH of the medium during the Obviously this technique is often used in parallelpurification of cocaine. For example Casale [86] with other methods in order to obtain the amount ofpoints out the phenomenon of epimerization in C-2 useful information necessary for a complete charac-position for ecgonine and ecgonine methyl ester terization of cocaine samples.when a strong base is employed. Della Casa and Martone [90] described a HPTLC

Other rearrangement in cocaine-related alkaloids method with direct ultraviolet densitometric mea-has been described [82] as results of benzoyl group surements of the components found in illicit drugmigration. samples. This methods provides also preliminary

So, it is evident that for cocaine comparative quantitative information about the relative amount ofanalysis many more substances can be considered as each component.marker compounds than those suggested for heroin.Nevertheless a complete cocaine characterization 3.2.2. Gas chromatography and GC–MSshould be carried out by also identifying other minor GC has certainly been one of the most usedcomponents such as residual solvents [87,89] and by techniques for the analysis of by-products and im-means of different analytical strategies. purities of illicit drugs. The chromatographic meth-

The origin impurities and manufacturing by-prod- ods developed for this purpose were first based onucts of cocaine are summarized in Scheme 2. packed columns [91,92]; however, due to the com-

plexity of the mixtures associated with the im-3.2. Analytical methods purities, the packed columns often did not give a

sufficient resolution. These problems have been3.2.1. Thin-layer chromatography and high- generally overcome by the use of capillary columns.performance thin-layer chromatography Amongst the detection methods employed, the most

In spite of the increasing availability of high- commonly used is FID [59,66,68], which has aefficiency chromatographic techniques, TLC con- sufficient sensitivity for the determination of manytinues to be considered by many authors as a useful by-products. For the determination of impuritiesinstrument for analysis and for comparative pur- present at lower concentrations, FID is often re-poses. placed by more sensitive detection methods such as

This kind of analytical technique is generally nitrogen–phosphorus (NPD) detection [68,69,78] orapplied to the detection of truxillines for example. ECD [77,93,94].


The combination of GC–MS [62,71,95,96] in the with low volatility and high molecular mass, HPLClast few years also represents a turning-point in this offers some advantage over GC for in-depth analysisfield. The analytical methods usually require a of cocaine [75,100].sample pre-treatment, including concentration [69] Le Belle et al. [101] proposed an easy HPLCand/or derivatization [97]. In this approach, as in analytical procedure, suitable for screening purposes,case of comparative analysis of heroin, problems due achieving the identification of major components,to the production of analytical artefacts [72] can cocaine impurities as well as adulterants in streetsometime arise. samples. The use of an ultraviolet detector operating

Generally speaking however, the chromatographic at two different wavelengths is proposed to bettertechniques in the gas phase seem to offer some evaluate the relative amount of these compoundsadvantages with respect to other analytical alter- respect to the cocaine content, obtaining suitablenatives, considering also the good standardization of results also for comparative purposes.the operative conditions and their diffusion in vari- The characterization of the truxillines was carriedous laboratories. out with reversed-phase HPLC using a UV detector

Using gas chromatographic techniques very accur- without any sample pre-treatment [102].ate results can be obtained with the identification and The cinnamoylcocaines, surely the most studiedquantification of marker impurities useful for com- substances in the comparative analysis of cocaineparative purposes [98]. The quantitative analysis of samples, were detected using ion-pair chromatog-the two cinnamoyl isomers indicating the difference raphy. By this technique partial resolution within the different varieties of Eritroxylon coca growing quantitative analysis of the cis and trans cinnamoyl-in different zones has been reported [91]. GC–MS cocaines, cocaine and tropococaine in extract of cocawas used also to highlight a higher concentration in leaves has been reported [64].the ENVN type with respect to cocaine of the ECVC The use of HPLC, has been also proposed for thetype [63]. analysis of diastereoisomers (pseudococaine, al-

In addition to the identification of minor alkaloids, lococaine and allopseudococaine) of cocaine. Thisthe analysis of the residual solvents through head- analytical procedures are useful to identify a possiblespace (HS) GC is often used for comparative analy- synthetic origin of the cocaine. Natural cocaine issis. This kind of investigation is really a complemen- constituted by the levo form of cocaine. The othertary technique for the characterization of the im- diastereoisomer can be only obtained by chemicalpurities due to processing [87–89]. The use of synthesis [103–107].nuclear magnetic resonance (NMR) for the quali-tative and quantitative determination of the solvents 3.2.4. Capillary electrophoresiswas also proposed [88]. Morello and Meyers sug- Micellar electrokinetic capillary chromatographygested the use of HS-GC and GC–MS with the use (MECC) is a promising analytical technique forof deuterated internal standards [87]. comparative cocaine analysis [108].

In the field of the analysis of the residual solvents CE was applied to study the relative ratio betweenthe technique based on solid-phase microextraction cinnamoylcocaine and cocaine [109] and the use of(SPME) has been recently described [99]. this ratio in comparative analysis of illegal sample

These studies demonstrate the actual employment has been established. According to this paper thein clandestine laboratories of acetates and chlorinated relative amount between cocaine and cinnamoyl-solvents during the production of cocaine other than cocaine could be related also to different geographicthe use of diethyl ether and acetone, for the prepara- origin. Consequently the evaluation of these parame-tion of cocaine hydrochloride. ters could give a taxonomic imprinting of great

value.3.2.3. High-performance liquid chromatography A review of the application of electrokinetic

HPLC is another analytical technique frequently capillary chromatography for the analysis of illicitused to obtain drug impurity signature profiles. drugs including heroin and cocaine has been recentlyOwing to the presence of many cocaine impurities published [110]. Due to its efficiency, high selectivi-


ty and general applicability, MECC is widely used 4. Conclusionsfor forensic drug analyses however systematic com-parative analyses carried out by this analytical It is common knowledge that chemical characteri-methods are still not referred. zation of illegal drugs can contribute the success of

the control of the illicit drug market.A variety of sophisticated chemical profiling pro-

3.3. New coca leaves alkaloids cedures have been described in the literature forcocaine and heroin analysis. By means of these

Owing the relevant interest in illicit drug ‘‘signa- procedure a wide number of drug-related compoundsture’’ and chemical profiling of minor components of can be identified in illicit samples and the value ofillicit cocaine samples many reports can be recently this approach has been recognised by numerous lawfound in the current literature regarding the identifi- enforcement institutions.cation of new coca leaves alkaloids. On this subject, for example, Casale stated ‘‘chro-

The characterization of these compounds seems to matographic impurities signature profiling analysisoffer a valid chance for comparative purposes. procedure determining if two or more exhibits of

For example, two hydroxycocaine have been cocaine came from the same batch would be aidentified in sample of seized cocaine [93], their tremendous benefit to law enforcement as an inves-identification was achieved through mass spectromet- tigative tool and can ultimately be used in Judicialric analysis as heptafluorobutyl and trimethylsilyl proceedings’’ [98] and his research group produced aderivatives. The concentration of these compounds large amount of scientific contribution in the field ofwas about 0.01% with respect to cocaine. The cocaine profiling.presence of these substances is surely an excellent Moreover it seems realistic to add that suchparameter for comparing the samples, but its limita- analytical tool would be successfully used world-tion is mainly due to the relevant complexity of the wide, with additional benefit to the international lawsample pre-treatment, that appears quite difficult to enforcement, only if a standardized and reproduciblestandardize. procedure will be used improving the analytical data

Casale and Moore [71], in a modification of the exchange between co-operating forensic laboratories.method proposed by Moore et al. [59], isolated four Unfortunately, some unresolved problems still exist.new compounds and their identification was done The main problems related to the selection of athrough a comparison of their mass spectrum with well standardized procedure can be summarized insome standard products synthesized. All four al- the following points: (a) identification of well definedkaloids have been quantified and resulted to be number and type of drug congeners useful forpresent in an amount lower than 0.1% with respect to comparative purposes; (b) standardization of thecocaine. procedure suggested for sample preparation, extrac-

Moore et al. [59] have recently published a review tion, concentration and derivatization before chro-of the literature data regarding in depth chromato- matographic analyses; (c) difficulty to unequivocallygraphic analysis of illicit cocaine and its precursors. chose a unique reliable chromatographic techniqueIn this review, attention is devoted to the characteri- and detection system able to resolve greater possiblezation of minor compounds and identification of new numbers of major and minor components of thealkaloids related to origin impurities (cuscohygrine, illicit drug; (d) global evaluation of results also inhygrine and 394959-trimethoxy-substituted coca al- terms of ageing of the samples, storage conditions,kaloids). sunlight exposition, infra-batch variability, analytical

Finally several new trace level alkaloids from artefacts and so on; (e) possibility of data com-Eritroxylon coca or by-products related to chlori- puterization, elaboration and cross-examination be-nated tropanes were identified in samples of illicit tween different laboratories.cocaine [111–115]. Even if it is possible to find in the current

These traces compound can be successfully used literature suitable analytical procedures able to en-in cocaine signature and comparative analysis. sure good analytical results, only one method gener-


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