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Fifty-two samples of street cocaine seized in the state of Rio de Janeiro, from May to April , were evaluated according to their purity, presence of inorganic and sugar diluents and concentration of pharmacologically active adulterants. Cocaine contents, as well as the adulterants caffeine, lidocaine and phenacetin, were evaluated by gas chromatography coupled with mass spectrometry. The samples were screened by Raman spectroscopy for the presence of inorganic diluents and carbohydrates. Freebase cocaine samples were majorly composed of pharmacological active compounds adulterants , unlike cocaine hydrochloride samples, which were majorly composed of inorganic compounds diluents. It could be observed, by Raman Spectroscopy associated to multivariate analysis, similarities on cocaine hydrochloride composition according to certain criminal gangs. Keywords: cocaine hydrochloride; freebase cocaine; cutting agents; chemical profiling; criminal gangs. Cocaine is one of the major alkaloid compounds found in leaves of plants from the Erythroxylum gender family Erythroxylaceae , mostly from the varieties Erythroxylum coca var. Cocaine is addictive and acts to inhibit the monoamine oxidase MAO enzyme, which is responsible for the degradation of monoamines, thereby affecting the reuptake of serotonin. It also stimulates the release of noradrenalin and dopamine, blocks sodium channels on peripheral nerves and is a potent anesthetic. Cocaine consumption also increases the strength and speed of cardiovascular contraction and provokes symptoms of euphoria and excitement. These properties make it one of the most commercialized drugs on the illicit market worldwide. Cocaine extraction is performed by acid-base extraction through immersion of coca leaves in acidic or alkaline solutions or by maceration with organic solvents. The refining process consists of oxidation, precipitation and successive dilutions for bleaching and purity increase. During these steps, many adulterants and diluents can be added in order to increase product volume and consequently the profit. Furthermore, street cocaine is frequently adulterated by local merchants, so that the materials seized on streets are generally less pure than the materials seized in the international airports. Cocaine is more commonly consumed in two different forms: freebase cocaine crack and cocaine hydrochloride cocaine HCl , though it can also be found in other forms, such as coca paste and merla. Crack is freebase cocaine, frequently found as little rocks, formed by the heating of cocaine hydrochloride with sodium bicarbonate in water. Street cocaine powder cocaine hydrochloride is water soluble, being usually snorted or injected. Since , Brazilian Federal Police, with aid from the United Nations Organization UNO , implemented the PeQui Project, which aims to analyze the chemical profile of drugs seized in Brazil, seeking origin characteristics and correlations among the seized samples. Many works have been published as a result of the PeQui Project, which could help to elucidate the characteristics of drugs seized in many states and identify the trends on the illicit market in Brazil. Justice , 54, Many of the studies published in the last years were concerning cocaine purity and the presence of pharmacological active adulterants. Bernardo et al. Drug Policy , 14, The presence of lidocaine was verified in 68 of the samples that were positive for caffeine. Diluents were identified by qualitative tests, in which carbonates and bicarbonates were identified in Maldaner et al. Cocaine commercialized in Brazil is usually originated from Bolivia, Peru or Colombia. In turn, cocaine also leaves Brazil for international trafficking, mainly to Africa, Europe and Asia. The degree of adulteration may vary according to geographical origin or availability of clandestine labs. O; Lordeiro, R. A; Augusti, R. Justice , 53, These findings could be related to the proximity of the Amazonas State with Colombia, one of the main cocaine producers. The presence of cocaine adulterants may vary according to place and time. Lidocaine and sugars were the two main cutting agents used in the s, while in the beginning of the s lidocaine was not detected in cocaine commercialized in Spain anymore. By the end of the s, lidocaine, caffeine and phenacetin were the main adulterants in cocaine commercialized in Italy. Diltiazem, hydroxyzine and levamisole were first reported from to in the United States and Europe. Nowadays, the main adulterants found in Europe are phenacetin, levamisole, caffeine, diltiazem, hydroxyzine and lidocaine, similar to what is found in Brazil. These spatiotemporal differences might be related to availability and price of the adulterants in certain areas. Souza et al. Justice , 56, The presence of phenacetin was observed only in the samples seized in , showing that this is a more recently used cutting agent. A higher degree of adulteration was observed in samples seized in the metropolitan region, suggesting a traffic route directed from the countryside to the capital. Raman spectroscopy and mass spectrometry are classified as category A most reliable , while spot tests are classified as category C least reliable. In this work, gas chromatography coupled with mass spectrometry was used for identification and quantification of pharmacological constituents, while Raman spectroscopy was used for identification of inorganic and sugar constituents. Screening the constituents on street cocaine is important for public health, as many of the substances added to cocaine can be harmful to users according to its dose and may interact both with cocaine and other drugs as well. Lidocaine, for instance, significantly potentiates cocaine-induced toxicity, increasing the convulsant potency of cocaine when consumed simultaneously. Caffeine also has synergic effects with cocaine, increasing the intensity and duration of cocaine symptoms, toxicity, convulsion rates and aggravation of cardiovascular problems. This study aims to evaluate the purity, the content of pharmacological active adulterants and the presence of inorganic and sugar diluents of fifty-two samples of cocaine in their two most consumed forms cocaine hydrochloride and freebase cocaine , seized in three different regions of Rio de Janeiro State City of Rio de Janeiro, Baixada Fluminense and Costa Verde and classified according to the labels of the three main criminal gangs found on the state. Thirty-three samples were seized in the city of Rio de Janeiro, five samples were seized in Baixada Fluminense, eleven samples were seized in Costa Verde and three samples were seized from unknown areas. The samples were kept in the dark and stored at room temperature until analysis. All standards were of analytical grade: caffeine, lidocaine and phenacetin standards were acquired from Sigma-Aldrich Chemie St. The spot tests Scott test, Wagner test and silver nitrate test , as well as the esterification tests, were performed on each sample in order to verify the presence of cocaine. The tests were also performed for each standard to indicate possible false-positive results. The samples and the standards were analyzed according to the method described by the United Nations Office on Drugs and Crimes Manual, 19 19 United Nations Office on Drugs and Crimes, Rapid testing methods of drugs of abuse: manual for use by national law enforcement and narcotics laboratory personnel, New York, USA, The formation of a blue precipitate indicates the presence of cocaine either salt or freebase. A brown precipitate indicates the presence of salt cocaine. The formation of a white or yellow precipitate indicates the presence of salt cocaine. Esterification test was performed in water bath, using a porcelain crucible for reacting a small quantity of the sample with five drops of concentrated sulfuric acid and the same volume of ethanol. The characteristic odor of ethyl benzoate, observed after around ten minutes of heat, is indicative of the presence of cocaine. The identification and quantification of adulterants present in each sample was carried out by the method proposed by Lapachinske et al. An aliquot of 5 mg of each sample was dissolved in methanol, followed by ultrasonic bath for 10 minutes and centrifugation for 3 minutes at rpm. An aliquot of the upper layer was collected and injected in a gas chromatographer coupled with mass spectrometry. Chromatographic separation was achieved on a VF-5ms fused-silica capillary column 30 m x 0. The carrier gas was helium and was used at a flow rate of 1. Each sample and the analytical reagents sodium carbonate, aluminum sulphate, sodium bicarbonate calcium carbonate, starch, sucrose, D-glucose, lactose and mannitol were individually inserted in a vial and directly analyzed by Raman spectroscopy. The analysis was performed using a FT Raman Bruker MultiRAM with laser source in nm near infrared , germanium detector cooled with liquid nitrogen, potency adjusted to mW, spectral range from to cm -1 , resolution of 4 cm -1 , performing 32 scans for cocaine samples and 16 scans for the standards. The samples were processed in ACD Labs software Toronto, Canada in order to compare them with the spectra obtained for each standard and to identify possible diluents. Due to its several processing steps, botanical characteristics and adulteration possibilities, cocaine composition can vary considerably according to its origin or manufacturer. Multivariate analysis plays an important role in characterizing the cocaine profile and establishes possible similarities among cocaine samples. All the samples analyzed in this work showed positive results on all presumptive tests. As expected, both cocaine powder and freebase cocaine showed positive results on Scott test, while only cocaine powder showed positive results on silver nitrate test, as shown in Figure 1. That is due to the chlorine atom present on cocaine hydrochloride, which combines to the silver ion to form silver chloride precipitate. Wagner test showed a deeper brown color for cocaine powder samples. Figure 1 Spot tests Scott test, silver nitrate test and Wagner test for three cocaine HCl samples and for three freebase cocaine samples. Blank: 1 for Wagner test, 2 for silver nitrate test and 3 for Scott test. Caffeine and phenacetin showed negative results in all spot tests. Lidocaine showed negative results on Wagner test, silver nitrate test and esterification test, however, it showed a positive result on the Scott test. Sodium carbonate showed a deep violet color and sodium bicarbonate showed a light violet color on Scott test and false-positive results on silver nitrate test. Sodium carbonate did not show as deep a yellow color as sodium bicarbonate did due to its low solubility in water. Starch showed a deep blue color in Wagner test due to interactions of the amylase helix with iodine ions Figure 2. Figure 2 Spot tests Scott test, silver nitrate test and Wagner test for the standards. The false positive result of lidocaine on the Scott test might be related to its structural similarities to cocaine. Both compounds have a tertiary amine that may interact with the cobalt ion from thiocyanate complex. This complex was prepared and its X-ray structure was recently described by Tabrizi and co-authors. The formation of a colored complex with Co II is not observed for caffeine or phenacetin. A; Mariotti, K. Also, the exceeding amount of sample used on the Scott test may lead to false-positive results. It was described by Tsumura and co-authors 22 22 Tsumura, Y. Therefore, the maximum sample weight should be up to 1 mg for a more precise result. All samples showed positive results for the esterification test. This is an important test to distinguish possible false-positive results, as common adulterants such as caffeine, lidocaine and phenacetin do not hydrolyze to ethyl benzoate. Though some presumptive tests can show false-positive results, they were able to detect the presence of cocaine in all the analyzed samples on this work minimum cocaine content of 1. Retention times obtained by the conditions used in this work, as well as the main peaks observed for each adulterant, are listed in Table 1. Freebase cocaine samples showed superior purity, with an average cocaine content of The average contents of cocaine and each pharmacological constituent, as well as their range, is described in Table 2. Figure 3 Histograms showing cocaine hydrochloride A and freebase cocaine B purity range. The percentage of the pharmacological compounds observed for each sample is shown in Figure 4. Figure 4 Cocaine and adulterant contents for each sample. Lapachinske et al. All samples analyzed by Lapachinske et al. That may explain their higher purity compared to the samples analyzed in this work, as street cocaine is often successively adulterated and diluted in order to increase profits. Researches indicate a high pharmacological interaction between cocaine and caffeine. When these compounds are associated, cocaine effects increase in intensity and duration. That may explain the presence of caffeine in most of the analyzed samples. Studies in rats showed that the combination of cocaine with caffeine also promotes an increase in toxicity, seizures and death rate. These samples did not show caffeine in composition, showed less phenacetin content The loadings graph showed that cocaine and phenacetin contents were the most important variables for the grouping of freebase cocaine samples, while caffeine and lidocaine contents were responsible the grouping of cocaine hydrochloride samples. At right, loadings graph showing the influence of each variable. Peak positions of the main Raman bands of the standards, found in this work, and their tentative vibrational assignments, based on literature data, are listed in Table 3. Aluminum sulphate, sodium carbonate, starch, lactose and mannitol were present in 4. It was only detected the presence of sodium bicarbonate in one of the eight freebase cocaine samples and it was not observed the presence of the other diluents in any other sample. Sucrose and D-glucose were not present in any cocaine hydrochloride or freebase cocaine sample. Calcium carbonate and sodium bicarbonate were mainly found associated in cocaine hydrochloride, corresponding to Samples showing calcium carbonate and sodium bicarbonate in a non-associated form corresponded to Figure 6 Frequency of each diluent in cocaine hydrochloride samples. Calcium carbonate and sodium bicarbonate are easily found in Brazilian local markets and are usually added to cocaine after it comes to Brazil, by local drug dealers. Calcium carbonate is a white, insoluble salt, used as a calcium supplement against osteoporosis, as a soil acidity regulator and in the manufacturing of mortar and cement. It is also commonly found in markets as chalk. Sodium bicarbonate is a white and soluble salt, easily found in drugstores due to its antacid property. As expected, it could be observed by PCA a clear discrimination of the cocaine hydrochloride samples and the freebase cocaine samples Figure 7 , indicating considerable differences on the profiles of cocaine HCl and freebase cocaine. Figure 7 Scores graph using intensity results obtained by Raman. No grouping tendencies were observed according to geographical origin samples seized in the city of Rio de Janeiro, Baixada Fluminense and Costa Verde , which may be related to the proximity of this areas. The three areas share borders and the samples were seized at approximately km 2 of maximum distance. It was not possible to verify grouping tendency for samples from the criminal gang C, possibly due to the low number of samples analyzed from this criminal gang. At right, HCA showing the grouping of freebase cocaine samples from criminal gang B. Besides the fact that drugs from different criminal gangs can come from different providers, the isolation of areas dominated by different criminal gangs can result in particular practices in drug processing and adulteration. Spot tests are useful for detecting the presence of cocaine in seized samples, even at low concentrations of cocaine from 1. Though lidocaine showed false-positive results on the Scott test, the association with other spot tests silver nitrate and Wagner tests , especially with esterification test, allowed for unambiguous identification of the presence of cocaine in the analyzed samples. Freebase cocaine showed considerably higher purity compared to cocaine hydrochloride, as well as different adulteration profile. Caffeine was the most frequent adulterant in cocaine hydrochloride samples, while phenacetin was found in all freebase cocaine samples. Open menu Brazil. Open menu. Text EN Text English. Presumptive tests The spot tests Scott test, Wagner test and silver nitrate test , as well as the esterification tests, were performed on each sample in order to verify the presence of cocaine. Gas chromatography The identification and quantification of adulterants present in each sample was carried out by the method proposed by Lapachinske et al. Raman spectroscopy Each sample and the analytical reagents sodium carbonate, aluminum sulphate, sodium bicarbonate calcium carbonate, starch, sucrose, D-glucose, lactose and mannitol were individually inserted in a vial and directly analyzed by Raman spectroscopy. Statistical analysis Due to its several processing steps, botanical characteristics and adulteration possibilities, cocaine composition can vary considerably according to its origin or manufacturer. Table 1 Retention times RT and main peaks observed for the standards. Table 2 Average content, standard deviation S. Table 3 Peak positions of the main Raman bands of the standards and their tentative vibrational assignments. Bruni, A. Lapachinske, S. Budavari, S. Yesinowski, J. Chem , 67 , Maldaner, A. Zacca, J. Justice , 54 , Botelho, E. Bernardo, N. Drug Policy , 14 , Justice , 53 , Justice , 56 , Gauvin, D. Derlet, R. Tabrizi, L. Chem , , Tsumura, Y. Marcelo, M. Schwarz, A. Penido, C. Forensic Sci. Boutasta, A. Raman Spectrosc. Roberts, S. Publication Dates Publication in this collection 27 May Date of issue This is an Open Access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Luiza D. Valeria C. Frances R. Bruno D. Marco Edilson F. Rosane N. Figures 8 Tables 3. Diluents Wavelength cm -1 Assignments 28 28 Penido, C. Starch Stay informed of issues for this journal through your RSS reader. PDF English. Google Google Scholar.
House delivery of drugs to wealthy customers is a profitable business in major cities. In Rio de Janeiro, this service costs US$ 20 per gram of cocaine. As.
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Beside the cocaine are baggies of compressed marijuana and crack rocks also being sold to a steady stream of customers. A dozen yards away, a young man drives up the dirt slum street on a motorcycle, an AR assault rifle with a grenade launcher strapped to his back. He makes no effort to hide the weapon. They are murderers. Brazilians smoke or snort about 90 tons of the disco powder a year, according to the United Nations Office on Drugs and Crime. But police have pushed out much of this blatant flouting of the law with a so-called pacification program, in which they storm into the favelas with overwhelming force and establish a permanent presence. The offensive started in , the year after Brazil was awarded hosting rights for the World Cup, and has steadily spread. In central favelas — which tourists might see — traffickers can no longer sell coke and pot so openly or carry assault rifles. One has to travel far out in the urban jungle to reach such scenes like the one in Antares. However, the pacification program has been criticized, with police accused of murdering some of the residents they are meant to be protecting. In April, a well-known dancer, Douglas Rafael da Silva, was shot dead in the Pavao Pavaozinho favela, provoking protests that turned into clashes. Pacification police patrol next to a mural of slain dancer Douglas Rafael da Silva in Pavao Pavaozinho. But witnesses in the Pavao Pavaozinho favela told GlobalPost that officers had shot at unarmed youths because they were smoking marijuana. One problem is that the authorities are failing to meet a promise to pair police suppression with new schools and investment in the slums, activists say. Back at the drug shop, Lucas oversees sales to dozens of customers handing over crumpled bills for bags or vials. With tired eyes, Lucas says he is finishing a hour shift. The drug point takes in thousands of dollars each day, he says, but as an employee of the Red Command he only makes a small percentage. Lucas says he has been involved in the drug trade since he was 12 and has been in countless gunfights with police. He tried to get out for a while, hoping to be a professional soccer goalkeeper. But he suffered an injury and took refuge back in the gang. A song comes on with lyrics cheering the drug dealers. Red Command! We want to hear your feedback so we can keep improving our website, theworld. Please fill out this quick survey and let us know your thoughts your answers will be anonymous. Thanks for your time! Young and old come out of ragged homes and shake their bodies to pulsating, distorted beats. Several gang members stand openly with their rifles, some dancing as they hold them. Tell us about your experience accessing The World. Take the survey.
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Drug users gather beneath an overpass in an area known as 'Cracolandia', or Crackland, in the Antares favela, in Rio de Janeiro, Brazil.
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