African Journal of Drug & Alcohol Studies, 14(1), 2015 Copyright
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African Journal of Drug & Alcohol Studies, 14(1), 2015 Copyright © 2015, CRISA Publications iDentifYing the coMPoSition of Street Drug NYAOPE usINg TwO Different MASS SPectroMeter MethoDS aye a. khine1, kebogile E. Mokwena2, Mempedi Huma2, lucy Fernandes2 1Department of Chemical Pathology, Medunsa/University of Limpopo, South Africa 2Department of Public Health, Medunsa/University of Limpopo, South Africa ABStrAct Criminalizaton of trading and using of street drug Nyaope has had challenges in South Africa due to controversies about its compositon. The high cost and complexity of its analysis using conventonal chromatography methods also limit the testng availability in most routne laboratories. A state of the Art method with simple specimen processing and faster turnaround tme at an afordable cost is urgently needed. To compare the ability of a new Time-of-Flight Mass Spectrometry with direct sample analysis (TOF-DSA MS) and Gas Chromatography Mass Spectrometry (GC-MS) methods in detectng the consttuents of Nyaope against turnaround tme and cost, in order to recommend a beter system for routne use. Cross-sectonal, qualitatve and descriptve pilot study on samples purchased from various sources of 12 townships in Northern Gauteng Province. The consttuents consistently detected in all samples were cafeine, drugs of abuse such as opiates, codeine, morphine, methyl-dioxy amphetamine (MDA) and heroin. Some samples contained antbiotcs (citrofex) and antretroviral drugs (zidovudine). Central nervous system (CNS) depressants such as phenobarbitone and benzodiazepines, benzitramide, moramide intermediates and thiofentanyl and stmulants such as Pipradol, and fenethyline were detected by the TOF-MS system. The usefulness of TOF-DSA MS was beter as a screening method while GC-MS provides specifcity and confrmatory detecton. Due to direct sample analysis, the TOF-DSA provides analytcal runtme of 15 sec while GC-MS takes 10 minutes per sample. The running cost for the GCMS is more expensive due to the high cost of reference materials and the need to perform specimen preparaton as opposed to TOF-MS. We recommend TOF-DSA MS for inital screening of organic compounds in the Nyaope mixtures followed by confrmaton by GC-MS for medico-legal interventons. Key words: Nyaope, drug of abuse, Mass Spectrometry, Gas Chromatography, Ant- retrovirals Corresponding author: Dr AA Khine, MBChB, MMed (Chemical Pathology), Department of Chemical Pathology, PO Box 227, Medunsa 0204, South Africa. Tel- 012-5214253, Fax- 012-5214157, Email- [email protected] KHINE ET AL. introDuction Nyaope, also known as whoonga, is a dangerous and highly addictve South Af- rican street drug (Department of Justce and Consituton SA, 2014). Nyaope is a fne brown powder due to its mixture with soil, sand or in some cases cement pow- der in order to disguise the underlying white power of drug of abuse. It is usually Figure 1. Nyaope sample wrapped in marijuana (dagga) leaves and smoked. It is not always clear what all of Nyaope frst appeared in the townships the ingredients of Nyaope are, and the in- around Durban in 2010, but is reportedly gredients may vary from sources of sellers. moving to impoverished areas around But one thing is clear: Nyaope is very ad- South Africa. Nyaope is a serious threat dictve and there are assumptons that it to South Africa’s HIV-positve populaton. may include heroin, detergent powder, rat There have been reports of gangs robbing poison, and crushed ant-retroviral drugs HIV/AIDS clinics in Soweto to obtain ARVs (ARVs) (Facts for Nyaope, 2014). ARVs are for making Nyaope, as well as addicted the medicatons used to treat patents users mugging ARV patents to obtain the with HIV. In most users, Nyaope not only drugs for themselves. It also promotes gives strong addicton but also severe ab- drug resistance to ARVs which has a huge dominal pain and seizures which are with- impact on the treatment programs for drawal symptoms. With respect to drug to patents living with HIV/AIDS (“Facts for drug interacton between various drugs of Nyaope,” 2014). Since Nyaope appears abuse, clinical studies showed that they similar to soil or cement powder, it is aggravate the body’s addictve reacton not easy to apprehend the users, sellers and also causes untoward efects such as or distributors. Analysis of Nyaope is not acute abdominal pain, seizures, vomitng, done routnely at medical laboratories or salivaton, psychosis etc (Bruce, Altce, forensic laboratories due to the high cost & Friedland, 2008). This makes the user and complexity of conventonal chroma- consume more and more Nyaope due to tography methods and lack of experience the belief that consuming more would re- in dealing with materials of such nature. lieve these symptoms. Nyaope is relatvely The newly introduced TOF-MS method cheap - about R20 to 30 for one “hit” and uses direct sample analysis and recent a person can become highly addicted af- studies showing its ability in identfying ter using the drug only once (Department individual compounds in the simulated of Justce and Consituton SA, 2014.). A mixture of drugs encourages the re- user will soon feel as if he needs several searchers to test its ability in the real drug hits to make it through the day. Untl and mixture samples (Wilhide, Lacourse, & unless the exact nature of the contents of Crowe, 2013) this street drug is understood, treatment The objectves of this study were to strategies and rehabilitaton support for identfy the exact consttuents of Nyaope the users may be difcult to achieve. by comparing the performance of two 50 COMPOSITION OF NYAOPE analytcal methods, namely the conven- Research and Development Laboratory tonal GC-MS (Gas Chromatography Mass in Midrand. All specimens were kept at Spectrometry) and the new TOF-MS (Time room temperature and cool dry place of Flight Mass Spectrometry). during transportaton to the laboratories. sample preparaton before analysis MAteriAl AnD MethoDS Gas Chromatography coupled Mass Spectrometry (GC-MS) is an internaton- Ethical approval for this study was ob- ally accepted analytcal comparatve tained from the Medunsa Research Ethics technique where compounds are sepa- Commitee (MREC/H/165/2012:IR). The rated in the gas phase and a characteristc research method applied was a cross-sec- patern (mass spectrum) of the separate tonal descriptve and comparatve study. compounds is obtained. Sample to be analysed, in a liquid form is injected into Sample an inert gas stream (helium/argon) and Nyaope samples were randomly col- swept into a column packed with a sta- lected through the users from the town- tonary phase inside the oven. Absorptve ships and urban areas surrounding Preto- interacton between the components in ria in North Gauteng. The samples were the gas stream and the coatng leads to a collected over a period of one week from diferental separaton of the components 12 areas in Gauteng province (with the of the mixture, which are then swept to number of samples collected from each the detector which is a Mass Spectrom- area shown in brackets); Pretoria central etry. Mass Spectrometry takes injected (5), Sunnyside (4), Mamelodi (10), Bronk- material, ionizes it in a high vacuum, pro- horstspruit (3), Delmas (2), Winterveld pels and focuses these ions and their frag- (2), Ramogodu (3), Springs (1), Tembisa mentaton products through a magnetc (4), Garankuwa (2), Soshanguve (2) and mass analyser and then collects and mea- Witbank (2). However, obtaining Nyaope sures the amounts of each selected ion samples was a challenge as it requires in a detector. When the interested com- building a relatonship with the current pounds are not volatle in gas, the process users in order to build their trust and ob- of sample derivitzaton has to be done tain their assistance. which is tme consuming and the need to Samples were collected in the sterile purchase the reference material for each 30 ml specimen jars and were labelled compound in the mixture makes the test- with the name of the area and the num- ing very expensive (Foltz, Fentman, & ber. Each specimen was thoroughly mixed Foltz, 1980) before dividing it into two containers. The In the TOF-MS method, a PerkinElmer frst container was marked A and the sec- FlexarTMFX-15 LC pump with AxIONTM ond one B. The lids were screwed tghtly TOF MS was used for analysis. It uses to prevent any leakage or contaminaton. direct sample analysis with no need for All samples labelled A were analysed at sample preparaton except extracton the GC-MS laboratory at the SAPS foren- in liquid Methanol for the organic com- sic toxicology and the specimens labelled pounds. The supernatant was analysed B were analysed at the Perkin Elmer through Time of Flight instrument by di- 51 KHINE ET AL. rect applicaton on the specimen grid. The eas under the peaks may be used to est- extracted specimens are carried through mate the amount of compound present. the TOF path by the Nitrogen gas fow Table 1 represents the qualitatve detec- in a fxed temperature and gas pressure ton of the various compounds found in environment. The calibrator, Acetonitrile the Nyaope samples that were analysed. liquid was used for checking the resolu- Although multple samples were collect- ton of this compound in an expected po- ed from most areas, representaton of siton and gamma hydroxyl butyric acid only one sample was chosen based on the was used as a blank to check the baseline highest number of compounds present. of separaton and peak areas (Daugherty Samples of Tembisa and Winterveld & Crowe, 2014) were not sufcient to share for GC-MS Molecular identfcaton of each com- laboratory hence we could not report the pound in the mixture is achieved by its spectra of drugs for these two areas done mass/charge (m/z) rato which is matched by GC-MS although the analyses of these to the best ft m/z in the isotopic paterns samples were done on the TOF-MS.