Using easy ambient sonic-spray ionization mass spectrometry (EASI-MS), fast and non-destructive fingerprinting identification and aging of ballpoint pen ink writings have been performed directly from paper surfaces under ordinary ambient conditions. EASI-MS data obtained directly from the ink lines showed that pens from different brands provide typical ink chemical profiles. Accelerated ink aging has also been monitored by EASI-MS revealing contrasting degradation behaviors for six different common ink dyes. As demonstrated for Basic Violet 3, some dyes display a cascade of degradation products whose abundances increase linearly with time thus functioning as 'chemical clocks' for ink aging. Analysis of questionable documents has confirmed the ink aging capabilities of EASI-MS. The order of superimposition at a crossing point has also been determined by EASI-MS. For two superimposed ink lines, continuous EASI-MS analysis has also shown that the EASI spray is able to penetrate through the layers and therefore both ink layers could be characterized.

Using two desorption/ionization techniques (DESI and EASI) and Brazilian real, US$ dollar, and euro bills as proof-of-principle techniques and samples, direct analysis by ambient mass spectrometry is shown to function as an instantaneous, reproducible, and non-destructive method for chemical analysis of banknotes. Characteristic chemical profiles were observed for the authentic bills and for the counterfeit bills made using different printing processes (inkjet, laserjet, phaser and off-set printers). Detection of real-world counterfeit bills and identification of the counterfeiting method has also been demonstrated. Chemically selective 2D imaging of banknotes has also been used to confirm counterfeiting. The nature of some key diagnostic ions has also been investigated via high accuracy FTMS measurements. The general applicability of ambient MS analysis for anti-counterfeiting strategies particularly via the use of "invisible ink" markers is discussed.

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Este é o primeiro trabalho que relata a ocorrência de resíduos de cocaína (COC) e benzoilecgonina (BE) em amostras coletadas em seis estações de esgoto diferentes (ETE) instaladas no Distrito Federal (DF) do Brasil. As concentrações de BE nos afluentes de esgoto foram utilizadas para calcular o consumo de cocaína (kg ano -1 por 1000 habitantes) em cada uma das regiões atendidas pelas ETE, em duas campanhas de amostragem (março e junho de 2010). Dentre as ETE estudadas, amostras provenientes de Samambaia apresentaram as maiores concentrações (de 3866 a 2477 ng L -1 de BE e 805 a 579 ng L -1 de COC) e doses por habitante (mais de 13 doses habitante -1 por ano). A extrapolação para toda a população do DF indica um consumo anual alcançando 1,0 tonelada de cocaína base livre, ou 1,1 tonelada de cloridrato de cocaína. Este trabalho também aborda a influência da forma de apresentação da cocaína (base livre ou sal cloridrato) e a integração com resultados de perfil químico na busca de estimativas mais realistas, principalmente no que se refere aos pontos de vista da criminalística e da segurança pública. 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.