Adriano O. Maldaner

Chemical profiling of cocaine seized by Brazilian Federal Police in 2009-2012: major Components

Perfis quimicos de cocaina podem fornecer informacoes relevantes para autoridades da area de seguranca publica. Desde 2006, a Policia Federal tem trabalhado em seu proprio perfil quimico de impurezas da cocaina (projeto PeQui). No esforco de estabelecer rotinas de perfil quimico, este trabalho descreve os resultados obtidos para identificacao de componentes majoritarios (pureza da cocaina, grau de oxidacao e farmacos utilizados como adulterantes), atraves da analise por cromatografia gasosa com detector de ionizacao de chama (GC-FID) de 210 amostras apreendidas em diferentes estados brasileiros entre 2009 e 2012. A pureza media observada para cocaina foi de 71% (expressa como base) e o grau de oxidacao, determinado pela medida relativa entre cis/trans-cinamoilcocaina e cocaina, mostrou-se dependente do local de apreensao. A maioria das amostras nao oxidadas foram apreendidas nos estados que fazem fronteira com os paises produtores. A forma de base livre e a mais comumente encontrada (59%) e mais de 50% das amostras analisadas nao apresentaram nenhum adulterante majoritario. Dentre os farmacos adulterantes identificados, fenacetina foi o mais abundante (30% das amostras). Levamisol, cafeina e lidocaina tambem foram identificados. O projeto PeQui tem sido utilizado regularmente para prover informacoes tecnicas cientificamente embasadas para a analise de inteligencia em seguranca publica e de dados estatisticos que podem contribuir para um melhor entendimento do trafico de cocaina.

LSD and 9,10-dihydro-LSD Analyses in Street Drug Blotter Samples via Easy Ambient Sonic-Spray Ionization MassSpectrometry (EASI-MS)

Normally, the identification of the LSD drug is performed by forensic laboratories, using the Ehrlich spot test. However, this is a nonspecific analysis. Additionally, the Brazilian Federal Police has identified the presence of a new compound in seized blotters: 9,10‐dihydro‐LSD, an uncontrolled substance. In this work, easy ambient sonic‐spray ionization mass spectrometry in the positive ion mode, EASI(+)‐MS, was used to characterize LSD and 9,10‐dihydro‐LSD compositions directly from the surface of blotters. The presence of LSD in the seized blotter samples were also confirmed via high‐performance liquid chromatography with ultraviolet detector. In a set of 41 blotters analyzed by EASI(+)‐MS, 28 showed positive results for LSD, seven for 9,10‐dihydro‐LSD, and another six samples showed negative results for both LSD and 9,10‐dihydro‐LSD. The combination of thin layer chromatography with EASI‐MS also demonstrated to be a relatively simple and powerful screening tool for forensic analysis of street drugs.

Brazilian Federal Police drug chemical profiling — The PeQui Project

Over the past six years the Brazilian Federal Police has undertaken major efforts in order to implement and to develop its own drug chemical profiling program. This paper aims to provide a broad perspective regarding the managerial strategies and some examples of subsequent technical issues involved in the implementation of such a project. Close collaboration with local drug enforcement and investigation teams, establishment of proper worldwide partnerships with well recognized institutions in the field of drug analysis and the attainment of suitable funding and human resources are shown to be key success factors. Some preliminary results concerning the chemical profile of cocaine seizures in Brazil during this process are presented.

Estimating cocaine consumption in the Brazilian Federal District (FD) by sewage analysis

This is the first report on the occurrence of cocaine (COC) and benzoylecgonine (BE) residues in six samples collected from different wastewater treatment plants (WTP) located in the Brazilian Federal District (FD). Concentrations of BE in the influent sewage were used to calculate cocaine consumption (kg year-1 per 1000 inhabitants) for each region attended by the WTP from two sampling campaigns (March and June, 2010). Among the WTP studied, samples from Samambaia showed higher concentrations (from 3866 to 2477 ng L-1 of BE and 805 to 579 ng L-1 of COC) and doses per inhabitants (more than 13 doses inhabitant-1 per year). The extrapolation to the whole FD population points out to an annual consumption reaching 1.0 ton of free base cocaine, or 1.1 tons of cocaine hydrochloride. The work also addresses the influence of the cocaine presentation form (free base or hydrochloride) and the integration with chemical profiling results in a more realistic estimate, mainly concerning the viewpoints of forensics and law enforcement.

Classification of Brazilian and foreign gasolines adulterated with alcohol using infrared spectroscopy

The smuggling of products across the border regions of many countries is a practice to be fought. Brazilian authorities are increasingly worried about the illicit trade of fuels along the frontiers of the country. In order to confirm this as a crime, the Federal Police must have a means of identifying the origin of the fuel. This work describes the development of a rapid and nondestructive methodology to classify gasoline as to its origin (Brazil, Venezuela and Peru), using infrared spectroscopy and multivariate classification. Partial Least Squares Discriminant Analysis (PLS-DA) and Soft Independent Modeling Class Analogy (SIMCA) models were built. Direct standardization (DS) was employed aiming to standardize the spectra obtained in different laboratories of the border units of the Federal Police. Two approaches were considered in this work: (1) local and (2) global classification models. When using Approach 1, the PLS-DA achieved 100% correct classification, and the deviation of the predicted values for the secondary instrument considerably decreased after performing DS. In this case, SIMCA models were not efficient in the classification, even after standardization. Using a global model (Approach 2), both PLS-DA and SIMCA techniques were effective after performing DS. Considering that real situations may involve questioned samples from other nations (such as Peru), the SIMCA method developed according to Approach 2 is a more adequate, since the sample will be classified neither as Brazil nor Venezuelan. This methodology could be applied to other forensic problems involving the chemical classification of a product, provided that a specific modeling is performed.

Correlation of cocaine hydrochloride samples seized in Brazil based on determination of residual solvents: an innovative chemometric method for determination of linkage thresholds.

Cocaine sample correlation provides important information in the identification of traffic networks. However, available methods for estimating if samples are linked or not require the use of previous police investigation and forensic expert knowledge regarding the number of classes and provide thresholds that are both static and data set specific. In this paper, a novel unsupervised linkage threshold method (ULT) based on chemometric analysis is described and applied to the analysis of headspace gas chromatography mass spectrometry (HS-GC/MS) data of more than 250 real cocaine hydrochloride samples seized by Brazilian Federal Police. The method is capable of establishing linkage thresholds that do not require any prior information about the number of classes or distribution of the samples and can be dynamically updated as the data set changes. It is envisaged that the ULT method may also be applied to other forensic expertise areas where limited population knowledge is available and data sets are continually modified with the inflow of new information.

Quantification of cocaine and its adulterants (lidocaine and levamisole) using the Dragendorff reagent allied to paper spray ionization mass spectrometry

Thin layer chromatography is a simple, easy and cheap technique widely used in Brazilian forensic laboratories, being a screening test for the separation and identification of illicit drugs, such as cocaine and its adulterants. Herein, paper chromatography using the Dragendorff reagent (revealing agent) was employed to analyze cocaine and its adulterants (levamisole, lidocaine, caffeine, and phenacetin). Positive results, i.e. visualization of the orange color, were only observed for cocaine, lidocaine and levamisole. Paper spray ionization mass spectrometry (PS-MS) was applied on revealed spots for the construction of a quantification model, for which some figures of merit were determined such as linearity, limit-of-detection (LOD), limit-of-quantification (LOQ) and accuracy. The results showed that PS-MS in positive-ion ionization mode, PS(+)-MS, is an efficient technique for direct analysis of the chromatographic spots on office-type paper revealed by the Dragendorff reagent. The method presented linearity greater than 0.98, and LODs of 6.51 μg mL−1 and 13.53 μg mL−1 for cocaine and levamisole, respectively, and 0.35 mg mL−1 for lidocaine. PS(+)MS was also applied to quantify cocaine in ten street crack samples, where there was no statistically significant difference between PS(+)MS and gas chromatography with flame ionization detection (GC-FID) data at a significance level of 5%.

Fast determination of cocaine and some common adulterants in seized cocaine samples by capillary electrophoresis with capacitively coupled contactless conductivity detection

The determination of cocaine and common adulterants in seized cocaine samples can be used to identify their possible production area and traffic routes. In this paper, capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D) was used for fast simultaneous determination of cocaine (COC), procaine (PRO), levamisole (LEV) and lidocaine (LID) (38 injections per hour). The separation was achieved using a fused silica capillary (50 cm total length − 40 cm effective length, 50 μm i.d.) and a background electrolyte composed of boric acid/3,4-dimethoxycinnamic acid (20/10 mmol L−1) with pH adjusted to 8.4 with sodium hydroxide. Linear working ranges (r ≥ 0.996) were obtained from 100 to 900 μmol L−1 for COC and from 50 to 450 μmol L−1 for PRO, LEV, and LID. The limits of detection were 10, 4, 6, and 7 μmol L−1 for PRO, COC, LEV and LID, respectively. In addition, the proposed method also provided adequate intra (≤2.3%) and inter-day (≤4%) precisions, as well as satisfactory recovery values for spiked seized cocaine samples (from 96% to 103%).

An external reference 1H qNMR method (PULCON) for characterization of high purity cocaine seizures

An external reference 1H qNMR method is developed and validated for the determination of three major alkaloids – cocaine, cis-cinnamoylcocaine and trans-cinnamoylcocaine – in high purity cocaine seizures. The method was applied to a set of 26 cocaine samples seized by the Brazilian Federal Police with cocaine contents ranging from approximately 63% to 94% (w/w) and cinnamoylcocaines ranging from 0.33% to 5.82% (w/w). The method enables the determination of these main alkaloids in 15 minutes of analysis with excellent accuracy (relative error <5% compared to the reference material certificate) and precision (RSD <3%). Some figures of merit are presented, including accuracy, recovery, repeatability, intermediate precision, stability, robustness, uncertainty, and limit of detection. The results show excellent correlation compared to the reference GC-FID methodology. It also permits the determination of the oxidation degree of samples. The method can be readily adapted to other analytes.

Drogas de abuso em águas naturais e residuárias urbanas: ocorrência, determinação e aplicações forenses

Drugs of abuse are commonly used outside medical or legal settings where their production, marketing and consumption are subject to legal summons and/or intervention. Classified as emerging contaminants, these substances have been recently detected in samples of environmental concern, such as waters and wastewaters. This review presents the state-of-the-art on the methodological approaches used in sample preparation, the main techniques applied in analytical determination at trace levels, as well as the use of information related to the drug or its metabolite concentration in sewage samples to empirically estimate the consumption of drugs of abuse in a city or region.