Optimization of HS-SPME/GC-MS analysis and its use in the profiling of illicit ecstasy tablets (Part 1)

A headspace solid-phase microextraction procedure (HS-SPME) was developed for the profiling of traces present in 3,4-methylenedioxymethylampethamine (MDMA). Traces were first extracted using HS-SPME and then analyzed by gas chromatography-mass spectroscopy (GC-MS). The HS-SPME conditions were optimized using varying conditions. Optimal results were obtained when 40 mg of crushed MDMA sample was heated at 80 °C for 15 min, followed by extraction at 80 °C for 15 min with a polydimethylsiloxane/divinylbenzene coated fibre. A total of 31 compounds were identified as traces related to MDMA synthesis, namely precursors, intermediates or by-products. In addition some fatty acids used as tabletting materials and caffeine used as adulterant, were also detected. The use of a restricted set of 10 target compounds was also proposed for developing a screening tool for clustering samples having close profile. 114 seizures were analyzed using an SPME auto-sampler (MultiPurpose Samples MPS2), purchased from Gerstel GMBH & Co. (Germany), and coupled to GC-MS. The data was handled using various pre-treatment methods, followed by the study of similarities between sample pairs based on the Pearson correlation. The results show that HS-SPME, coupled with the suitable statistical method is a powerful tool for distinguishing specimens coming from the same seizure and specimens coming from different seizures. This information can be used by law enforcement personnel to visualize the ecstasy distribution network as well as the clandestine tablet manufacturing.

Abordagem Bayesiana da curva de lactação de cabras Saanen de primeira e segunda ordem de parto

O objetivo deste trabalho foi utilizar o método Bayesiano no ajuste do modelo de Wood a dados de produção de leite de cabras da raça Saanen. Dois grupos de animais da primeira e segunda lactação foram considerados. Amostras das distribuições marginais a posteriori dos parâmetros do modelo de Wood e das funções de produção derivadas desses parâmetros - pico de produção, tempo do pico de produção, persistência e produção total de leite - foram obtidas pelo algoritmo Gibbs Sampler. As inferências foram feitas em cada população e os resultados mostraram diferenças na taxa de decréscimo da produção após o pico e na persistência, indicando maior produção nos animais de segunda lactação. Realizou-se um estudo de simulação de dados para avaliar o método Bayesiano sob diferentes estruturas de matrizes de covariâncias dos parâmetros. Os resultados desse estudo indicam que o método é eficiente no estudo das curvas de lactação quando a matriz de covariância apresenta alta correlação dos parâmetros.

Graphitized carbon black in quartz tubes for the sampling of indoor air nicotine and analysis by microwave thermal desorption-capillary gas chromatography

Nicotine in a smoky indoor air environment can be determined using graphitized carbon black as a solid sorbent in quartz tubes. The temperature stability, high purity, and heat absorption characteristics of the sorbent, as well as the permeability of the quartz tubes to microwaves, enable the thermal desorption by means of microwaves after active sampling. Permeation and dynamic dilution procedures for the generation of nicotine in the vapor phase at low and high concentrations are used to evaluate the performances of the sampler. Tube preparation is described and the microwave desorption temperature is measured. Breakthrough volume is determined to allow sampling at 0.1-1 L/min for definite periods of time. The procedure is tested for the determination of gas and paticulate phase nicotine in sidestream smoke produced in an experimental chamber.

Ilmakehan hiukkasmaisten ioniyhdisteiden online-mittaus

Ilmakehän hiukkaset aiheuttavat merkittäviä ympäristö- ja terveyshaittoja, joihin vaikuttaa hiukkasten kemiallinen koostumus. Hiukkasten kemiallisesta koostumuksesta voidaan hankkia tietoa hiukkasmittauksilla. Työn tavoitteena oli rakentaa jatkuvatoiminen mittausjärjestelmä, jolla voidaan mitata ilmakehän aerosolihiukkasten ionipitoisuuksia. Mittausjärjestelmä koostuu virtuaali-impaktorista, denuderputkista, PILS-laitteesta ja ionikromatografista. Näyteilmavirtaus kulkee ensin esierottimena toimivan virtuaali-impaktorm lävitse, joka poistaa aerodynaamiselta halkaisijaltaan 1,3 um:a suuremmat hiukkaset ilmavirtauksesta. Näyte, joka sisältää 1,3 um:a pienemmät hiukkaset kulkee virtuaali-impaktorin jälkeen kahden 1 % KOH-liuoksella käsitellyn denuderputken lävitse, joilla poistetaan hiukkasmääritystä häiritsevät happamat kaasut näytevirtauksesta. Denuderputkien jälkeen ilmavirtaus saapuu PILS-laitteeseen, jossa hiukkaset kasvatetaan vesihöyryn avulla aerosolipisaroiksi, törmäytetään keräyslevyyn ja sekoitetaan sen jälkeen sisäistä standardiainetta (NaBr) sisältavään kuljetusliuokseen. Kuljetusliuoksen ja aerosolipisaroiden seoksesta koostuva näyteliuos johdetaan PILS-laitteesta ionikromatografille analysoitavaksi. Mittausjärjestelmään liitetyllä ionikromatografilla voidaan analysoida neljä näytetta tunnissa. Näytteistä määritettävät anionit olivat sulfaatti, nitraatti ja kloridi. PILS-mittausjärjestelmää testattiin keräämällä hiukkasnäytteitä samanaikaisesti PILS-laitteella sekä virtuaali-impaktorilla tai suodatinkeräimellä ja vertaamalla saatuja aerosolihiukkasten sulfaattipitoisuuksia keskenään. Testeissa kerättiin joko VOAG-laitteella tuotettuja ammoniumsulfaattihiukkasia tai laboratorion huoneilmaa. PILS-mittausjärjestelmällä mitatut sulfaattipitoisuudet olivat 2-20 % pienempia kuin suodatinkeraimella mitatut, kun kerättiin keinotekoisesti tuotettuja ammoniumsulfaattihiukkasia. Huoneilmaa kerättäessä PILS-mittausjärjestelmällä saadut pitoisuudet olivat noin 10 % pienempiä kuin suodatinkeräystulokset. Koetulokset osoittivat, että mittausjärjestelmällä saadaan analysoiduksi luotettavasti hiukkasten sulfaattipitoisuudet.

Hakevirrasta otettavan näytteen luotettavuus ja näytteenottimen kehittäminen

Työn tavoitteena oli saada tietoa yleisesti partikkelivirtauksessa tapahtuvasta näytteenotosta ja näytteenottomenetelmistä. Työssä tutkittiin UPM-Kymmenen Kaukaan tehtaan nykyisen ostohakkeen automaattisen näytteenottimen toimintaa sekä sen ottamien näytteiden luotettavuutta kokeellisesti ja tilastollisesti. Lopuksi tutkimuksessa ideoitiin uusi näytteenottimen konstruktio. Uuden konstruktion suunnittelun lähtökohtana oli, että näytteenottimen konstruktiolla tulisi voida ottaa toistuvasti ja turvallisesti luotettavia hakenäytteitä aiheuttamatta muulle vastaanottoaseman toiminnalle häiriöitä Tutkimusta varten tehtiin eri haketoimittajien kanssa koenäytteenottoja. Hakenäytteet otettiin kolmessa eri haketoimituksen vaiheessa niiden keskinäistä vertailua varten. Hakenäytteistä määritettiin kuiva-ainepitoisuus ja laatuanalyysin tekoa varten palakokojakauma koeseulonnoilla. Palakokojakauma-analyysistä saatuja jakaumapainoprosenttiosuuksien ja niistä laskettujen laatuarvojen pohjalta tutkittiin automaattisen näytteenottimen ottaman näytteen luotettavuutta ja näytteenottimen toimintaa. Konstruointityössä noudatettiin pääpiirteittäin ohjeistoa VDI 2221. Uuden näytteenottimen suunnittelutyön tavoitteet määriteltiin tutkimuksessa tehtyjen päätelmien ja kokeiden pohjalta. Uudelle näytteenottimen konstruktiolle etsittiin toteutuskelpoisia ratkaisuja jo olemassa olevista laitteistoista ja uusista ideoista. Uudet konstruktiovaihtoehdot suunniteltiin noudattamaan näytteenottoteoriaa ja sijoituspaikan asettamia vaatimuksia.

Método colorimétrico para determinação de dióxido de nitrogênio atmosférico com preconcentração em coluna de c-18

An alternative analytical method for nitrogen dioxide (NO2) in atmosphere was developed. The collection of NO2 is performed by a Sep-Pack C-18 cartridge impregnated with 11% (v/v) of triethanolamine plus 3,6 % (v/v) of ethylene glycol plus 25 % (v/v) of acetone combined solution. When the impregnating is used, NO2 is collected with good repeatibility (CV = 3,3 %). The NO2 absorbed in the sampler was stripped from the sorbent with a methanol 5% (v/v) aqueous solution and was determined by colorimetry as nitrite by using the Griess-Saltzman reagent. The detection limit of 1,4 ppb for 60 min sampling at 0,5 L min-1 flow rate was obtained. Preparation and conditioning procedures for TEA-C-18 cartridge, sampling flow rate, absorption capacity and interference of other species are discussed.

Amostragem passiva de poluentes atmosféricos: aplicação ao SO2

The passive sampling technique has been widely used for many years in the measurement of personal exposure to pollutantes in the workplace. In recent years the technique has been used too for measurements in ambient air. In the specific case of SO2 a variety of passive samplers have been described in the literature. The great number are diffusive samplers and some few are permeation samplers. They are basically of two types: badge and tube-type. However there are more than 10 variations in relation to the sampler dimensions, diffusion barriers and pollutant sorption medium. The technique trend to be very used in the near future with samplers able to reach very low detection limits, proposing a viable option for monitoring specific species at urban, regional and global scales.

Análises seqüenciais de agrupamentos aplicadas ao estudo de partículas atmosféricas

The present paper has as objective to apply a sequential Cluster Analysis to the atmospheric particles: Hierarchical Cluster Analysis followed by Nonhierarchical Cluster Analysis. The hierarchical cluster analysis results were used as start point for the nonhierarchical cluster analysis as an agglomerative technique. These particles were taken from two areas of the metropolitan region of Porto Alegre, Charqueadas and Sapucaia do Sul., from may /97 to may/98, using a High Volume Sampler (Hi-Vol). Around 10,000 particles were analysed by Scanning Electron Microscope with Energy-Dispersive X-Ray microanalysis (SEM-EDS). The Hierarchical Cluster Analysis allowed the identification of five groups of particles, whose amounts were differentiated according to the summer and the winter campaigns. The abundance of each type of particles inside each group according to the different sections was verified by the Nonhierarchical Cluster Analysis, resulting in information about the emissions sources. The groups of particles of Si/Al and Si and of Fe/Zn and Fe for Charqueadas were more significant in section 2 and 3 (NW and W wind directions) and in section 1 (SE wind direction), evidencing the influence of the coal power plant and steel industry, respectively located in these quadrants. In Sapucaia do Sul the data were more heterogeneous, causing a certain difficulty to identify the source as anthropogenic. Nevertheless the group of particles containing Fe was found in sectors of NW/W wind directions which shows the influence of the steel plant.

Aplicação da CLAE para determinação do ácido 10-Hidróxi-2-decenóico (10-HDA) em geléia real pura e adicionada a mel brasileiro

The aim of this paper was to determine the 10-HDA in pure royal jelly and products containing royal jelly, using HPLC methodology. 10-HDA is the natural indicator of the presence of royal jelly in products and also gives the authenticity of pure royal jelly. The chromatographic conditions used were: isocratic system, C18-H column, auto sampler, diode array UV-VIS detector (225 nm), mobile phase with methanol/water (45:55), pH= 2.5 and a-naphtol as internal standard. The results obtained using laboratory samples for pure royal jelly were 2.37%, varying from 0.15% for honey with 10% of royal jelly to 2.10% for honey with 90% of royal jelly respectivelly. For commercial products, the 10-HDA content varied from no detectable to 0.026%. The recovery test presented a minumum of 100.44% The detection limit was 45.92 ng/mL and the quantification limit was 76.53 ng/mL.

Comparação de duas metodologias de amostragem atmosférica com ferramenta estatística não paramétrica

In atmospheric aerosol sampling, it is inevitable that the air that carries particles is in motion, as a result of both externally driven wind and the sucking action of the sampler itself. High or low air flow sampling speeds may lead to significant particle size bias. The objective of this work is the validation of measurements enabling the comparison of species concentration from both air flow sampling techniques. The presence of several outliers and increase of residuals with concentration becomes obvious, requiring non-parametric methods, recommended for the handling of data which may not be normally distributed. This way, conversion factors are obtained for each of the various species under study using Kendall regression.

Construção de amostrador passivo de baixo custo para determinação de dióxido de nitrogênio

A new passive sampling system for monitoring NO2 in air has been developed to measure gas concentrations in indoor and outdoor air. The sampler is inexpensive, and easy to construct and operate. Nitrogen dioxide forms a derivative after reaction with a filter coated with triethanolamine and ethyleneglycol. The nitrogen dioxide derivative is extracted from the filter, and the concentration is determined by colorimetry. To test the sampler for measuring ambient level nitrogen dioxide, measurements were carried out inside homes and in a range of workplace environments.

Desenvolvimento e aplicação de sistema passivo de coleta de poluentes atmosféricos para monitoramento de Cd, Cr, Pb, Cu, Fe, Mn, Zn e particulados totais

The objective of this study was to assess a new monitoring technique of particulate and trace metals in the atmosphere via the use of a passive sampler of air pollutants in the city of Goiânia. The average particulate weight and average concentrations of metals Fe, Cr, Zn, Pb, Cu, Mn, and Cd were 0.1104 g and 257.5; 23.4; 17.8; 6.7; 1.9; 0.8; 0.2 μg/m²/day, respectively. Higher Pb and Cr concentrations were obtained in areas with intense traffic. This study revealed that it is possible to monitor trace metals with passive sampling, developed at a low cost and operational facility.

Desenvolvimento e avaliação de um porta-amostra de baixo custo para caracterização elétrica de materiais cerâmicos

Conventional sample holder cells used to the electric characterization of ceramics at high temperature consists of an alumina tube and platinum wires and plates using a complex design. The high cost materials used in the conventional sampler holder cell were replaced by stainless steel and conventional ceramics. The sample holder was validated by characterizing yttria-stabilized-zirconia in a temperature range of 25 to 700 ºC. The results do not present variations, discontinuity or unusual noise in the electric signals. Several samples were characterized without maintenance, which demonstrates that the sample holder is electric and mechanic adequate to be used to electrical characterization of ceramics up to 700 ºC.

Quantificação de conídios de Pyricularia grisea no plantio direto e convencional de arroz de terras altas

Foi estudada a liberação de conídios de Pyricularia grisea no plantio convencional (PC) e direto (PD) de arroz (Oryza sativa) de terras altas, nas fases de desenvolvimento vegetativo e emissão de panículas nos experimentos de campo realizados em dois anos (1998/2000). As coletas de conídios de P. grisea foram realizadas com as armadilhas volumétricas Rotorod sampler. Objetivando quantificar os conídios viáveis e com potencial para causar infecção em folhas novas foram também utilizadas bandejas com plantas de arroz com 25 dias de idade das cultivares Carajás e Primavera expostas no campo, como armadilhas vivas. Na safra 1998/1999, o número de conídios de P. grisea aumentou linearmente com o tempo, entre o estádio de grão pastoso e maduro. Na safra de 1999/2000, a quantidade de conídios coletada aumentou de maneira exponencial, iniciando ao final do estádio emborrachamento até na fase de grão semi-maduro. O número de conídios coletados com a armadilha volumétrica diminuiu exponencialmente com o aumento da precipitação pluviométrica, assim como, reduziu a severidade da brusone nas plantas da armadilha viva tanto para a cultivar Carajás como para Primavera. A produção e a liberação de conídios foi menor no plantio direto tanto na fase vegetativa como durante o enchimento dos grãos nas panículas.

Influência da adubação nitrogenada, época de plantio e aerosporos sobre a severidade da mancha de grãos em arroz de terras altas

A mancha de grãos (MG) ocupa o segundo lugar em importância econômica entre as doenças do arroz. Foi estudada a influência de níveis de adubação nitrogenada, época de plantio e concentração de esporos no ar sobre a severidade da doença no campo. A severidade de MG, na cultivar BRS Bonança, foi avaliada em duas épocas de plantio (30/11/2006 e 21/12/2006) e cinco doses de adubação nitrogenada (0, 30, 60, 120 e 240 kg de N.ha-1) utilizando o delineamento experimental de blocos ao acaso em esquema de parcelas subdivididas com três repetições. O efeito de dose de N sobre a severidade de MG não foi significativo. A correlação entre a severidade de MG e espiguetas vazias foi positiva e significativa. A população de fungos no ar (aerosporos) foi quantificada utilizando armadilhas volumétricas, Rotorod Sampler, desde a emissão até o amadurecimento das panículas. A mancha de grãos aumentou linearmente com tempo (r = 0,98; P < 0,01), o mesmo não ocorreu com o aumento total de fungos que variou de 0,23 a 2,97 esporos/litro de ar/minuto. Os fungos presentes no ar em ordem decrescente de concentração foram Nigrospora sp., Pyricularia oryzae, Pithomyces sp., Alternaria sp., Cercospora sp., Fusarium sp., Curvularia sp. e Bipolaris sp. Estes fungos e Phoma sp. entre outros também foram detectados no teste de sanidade de sementes. A correlação entre a quantidade de esporos de P. oryzae e outros fungos foi linear e positiva (r = 0,80, P < 0,01). O número de esporos aumentou com o aumento da umidade relativa e diminuiu com o aumento da temperatura máxima de maneira exponencial.